EP0779306B1 - Process for preparation of cycloolefin copolymers - Google Patents

Process for preparation of cycloolefin copolymers Download PDF

Info

Publication number
EP0779306B1
EP0779306B1 EP96119751A EP96119751A EP0779306B1 EP 0779306 B1 EP0779306 B1 EP 0779306B1 EP 96119751 A EP96119751 A EP 96119751A EP 96119751 A EP96119751 A EP 96119751A EP 0779306 B1 EP0779306 B1 EP 0779306B1
Authority
EP
European Patent Office
Prior art keywords
dimethylamido
propylidene
bis
indenyl
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96119751A
Other languages
German (de)
French (fr)
Other versions
EP0779306A3 (en
EP0779306A2 (en
Inventor
Michael Dr. Riedel
Thomas Dr. Weller
Alexandra Dr. Jacobs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ticona GmbH
Mitsui Petrochemical Industries Ltd
Original Assignee
Ticona GmbH
Mitsui Petrochemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ticona GmbH, Mitsui Petrochemical Industries Ltd filed Critical Ticona GmbH
Publication of EP0779306A2 publication Critical patent/EP0779306A2/en
Publication of EP0779306A3 publication Critical patent/EP0779306A3/en
Application granted granted Critical
Publication of EP0779306B1 publication Critical patent/EP0779306B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to a method for producing a Cycloolefin copolymers in the presence of a metallocene compound.
  • Metallocene compounds of subgroup 4 of the periodic table of the Elements are active in combination with methylaluminoxane (MAO) Catalysts for the polymerization of olefins. It is from the literature Production of polyolefins with soluble metallocene compounds in Combination with aluminoxanes or other cocatalysts due to their Lewis acidity convert the neutral metallocene into a cation and can stabilize, known (EP-A-129 368).
  • MAO methylaluminoxane
  • Metallocenes and half-sandwich complexes are not just about Polymerization or oligomerization of olefins of great interest. she can also be used as hydrogenation, epoxidation, isomerization, C-C coupling catalysts are used (Chem. Rev. 1992, 92, 965-994).
  • EP 0659758 relates to a stereorigid metallocene compound, which as Ligands at least two substituted or unsubstituted Cyclopendadienyl groups has a mono- or polycyclic Ring system are interconnected, at least one Cyclopentadienyl group on the mono- or polycyclic ring system is fused and a process for the preparation of a cycloolefin copolymer.
  • the cycloolefin copolymers obtained in this way have high tear strengths and are suitable for the production of extrusion parts and injection molded articles.
  • the task was to develop an economical process for the production of To provide cycloolefin copolymers. This task is accomplished by solved the present invention.
  • the present invention thus relates to a process for the preparation of a cycloolefin copolymer by polymerizing at least one cyclic olefin and at least one acyclic olefin, in the presence of a catalyst comprising at least one metallocene compound of the formula I, wherein L and L 'is a substituted or unsubstituted cyclopentadienyl group, T is a bridge between L and L', and means [R 5 R 6 X] n , where X is independently the same or different carbon, silicon, germanium or tin, which R 5 and R 6 independently represent a hydrogen atom or a C 1 -C 30 hydrocarbon radical, and n represents 1, 2, 3 or 4, M is a tetravalent transition metal, and R 1 , R 2 , R 3 and R 4 independently of one another, the same or different, is a hydrogen atom or a C 1 -C 20 hydrocarbon radical.
  • M is titanium, zirconium or hafnium.
  • R 5 and R 6 advantageously denote a hydrogen atom, C 1 -C 20 alkyl or C 6 -C 20 aryl, and n is preferably 1 or 2.
  • T preferably denotes carbon, silicon, germanium or tin.
  • R 1 and R 3 are, independently of one another, identical or different, a hydrogen atom or a C 1 -C 20 hydrocarbon radical, preferably a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 14 aryl, in particular Methyl.
  • R 2 and R 4 are independently the same or different and preferably a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 14 aryl, especially methyl.
  • radicals R 1 , R 2 , R 3 and R 4 are independently the same or different.
  • the radicals R 1 , R 2 , R 3 and R 4 are preferably identical and are a C 1 -C 20 alkyl or C 6 -C 14 aryl, in particular methyl.
  • a metallocene compound of the formula (II) is used in the process according to the invention, and a metallocene compound of the formula (II) is used according to the process of the invention wherein Cp denotes an unsubstituted or substituted cyclopentadienyl group, Ind denotes unsubstituted or substituted indenyl, M denotes a tetravalent transition metal, R 1 , R 2 , R 3 and R 4 are independently the same or different and a hydrogen atom or a C 1 -C 20 - Are hydrocarbon radical, R 5 and R 6 are independently the same or different and represent a hydrogen atom or a C 1 -C 30 hydrocarbon radical.
  • M is titanium, Zirconium or hafnium.
  • Ind is unsubstituted or substituted indenyl.
  • substituted Indenyl are: 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthyl-indenyl, 2-methyl-4-isopropyl-indenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl- ⁇ -acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl.
  • R 5 and R 6 are, independently of one another, identical or different, preferably identical, and a hydrogen atom or a C 1 -C 30 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 20 aryl.
  • R 5 and R 6 are preferably methyl or phenyl, in particular methyl.
  • R 1 and R 3 are, independently of one another, identical or different, a hydrogen atom or a C 1 -C 20 hydrocarbon radical, preferably a C 1 -C 20 hydrocarbon radical, such as C 1 -C 20 alkyl or C 6 -C 14 aryl, especially methyl.
  • R 2 and R 4 are independently the same or different and preferably a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 14 aryl, especially methyl.
  • the radicals R 1 , R 2 , R 3 and R 4 are independently the same or different.
  • the radicals R 1 , R 2 , R 3 and R 4 are preferably the same and a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or rC 6 -C 14 aryl, in particular methyl.
  • the metallocene compound of the formula I or II can be prepared by reacting a compound of the formula III, in which L is a ⁇ ligand, L 'is a ⁇ ligand, T is a bridge and m is 1 or 2, with a compound of the formula IV, wherein M is a tetravalent metal, and R 1 , R 2 , R 3 and R 4 independently of one another are identical or different and represent a hydrogen atom or a C 1 -C 20 hydrocarbon radical
  • the reaction is preferably carried out in an aprotic solvent, e.g. toluene or hexane.
  • the temperature can be between -78 and 140 ° C amount, preferably 0 ° C to 110 ° C.
  • the compound of formula III can Excess are used, 1 equivalent of the compound are preferred of the formula III and 1 equivalent of the metal tetramide of the formula IV used.
  • a catalyst is preferably used in the process according to the invention, the at least one metallocene compound of the formula I and at least one Contains cocatalyst. Mixtures of two or more can also be used Metallocene compounds are used, in particular for the production of Reactor blends or of cycloolefin copolymers with broad or multimodal Molecular weight distribution.
  • each is a cocatalyst in the process according to the invention Compound suitable because of its Lewis acidity the neutral Can convert metallocene compound into a cation and stabilize it ("unstable coordination").
  • the cocatalyst, or that of it formed anion do not undergo any further reactions with the cation formed (EP-A-427 697).
  • An aluminum compound is preferred as the cocatalyst and / or a boron compound is used.
  • the boron compound preferably has the formula R a x NH 4-x BR b 4 , R a x PH 4-x BR b 4 , R a 3 CBR b 4 or BR b 3 , where x is a number from 1 to 4, preferably 3 , means the radicals R a are the same or different, preferably the same, and are C 1 -C 10 alkyl or C 6 -C 18 aryl, or two radicals R a together with the atoms connecting them form a ring, and the R b radicals are the same or different, preferably the same, and are C 6 -C 18 aryl, which can be substituted by alkyl, haloalkyl or fluorine.
  • R a is ethyl, propyl, butyl or phenyl and R b is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP-A-277 003, EP-A-277 004 and EP-A- 426 638).
  • An aluminum compound such as aluminoxane is preferred as the cocatalyst and / or an aluminum alkyl used.
  • An aluminoxane in particular of the formula Va for the linear type and / or of the formula Vb for the cyclic type, is particularly preferably used as cocatalyst, where in the formulas Va and Vb the radicals R c are identical or different and are hydrogen or a C 1 -C 20 hydrocarbon group such as a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group or benzyl and p is a is an integer from 2 to 50, preferably 10 to 35.
  • radicals R c are preferably the same and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.
  • radicals R c are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in a proportion of from 0.01 to 40% (of the radicals R c ).
  • the processes for producing the aluminoxanes are known.
  • the exact spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings become closed connect larger two-dimensional or three-dimensional structures.
  • all aluminoxane solutions are one changing content of unreacted aluminum starting compound, which in free form or as an adduct, together.
  • metallocene compound in the Polymerization reaction with a cocatalyst, especially one Pre-activate aluminoxane. This makes the polymerization activity clear elevated.
  • the preactivation of the metallocene compound is preferably in Solution made.
  • the metallocene compound is preferred in one Solution of the aluminoxane dissolved in an inert hydrocarbon.
  • Inert hydrocarbon is an aliphatic or aromatic Hydrocarbon. Toluene is preferably used.
  • the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case based on the total amount of solution.
  • the metallocene compound can be used in the same concentration, but it is preferably used in an amount of 10 -4 to 1 mol per mol of aluminoxane.
  • the preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. One works at a temperature of -78 to 150 ° C, preferably 0 to 80 ° C.
  • the metallocene compound is preferably used in a concentration, based on the transition metal, of 10 -3 to 10 -8 , preferably 10 -4 to 10 -7 mol, transition metal per dm 3 solvent or per dm 3 reactor volume.
  • the aluminoxane is preferably used in a concentration of 10 -6 to 10 -1 mol, preferably 10 -5 to 10 -2 mol per dm 3 of solvent or per dm 3 of reactor volume.
  • the other cocatalysts mentioned are used in approximately equimolar amounts to the metallocene compound. In principle, however, higher concentrations are also possible.
  • the aluminoxane can be prepared in various ways by known methods.
  • One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene).
  • an inert solvent such as toluene
  • two or more different aluminum trialkyls are reacted with water, for example in accordance with the desired composition (S. Pazynkiewicz, Polyhedron 9 (1990) 429, EP-A 302 424).
  • all aluminoxane solutions are one changing content of unreacted aluminum starting compound, which in free form or as an adduct, together.
  • Cleaning is required to remove catalyst poisons present in the olefin with an aluminum compound, preferably an aluminum alkyl, such as Trimethyl aluminum or triethyl aluminum, advantageous. This cleaning can both take place in the polymerization system itself, or the olefin is before Added to the polymerization system with the aluminum compound in contact brought and then separated again.
  • an aluminum compound preferably an aluminum alkyl, such as Trimethyl aluminum or triethyl aluminum
  • the metallocene compound is preferred in the process according to the invention with the cocatalyst outside the polymerization reactor in one separate step using a suitable solvent. Carrying can be carried out.
  • solvent is added to the reaction mixture, then it is common inert solvents such as aliphatic or cycloaliphatic Hydrocarbons, petrol or hydrogenated diesel oil fractions or toluene.
  • the metallocene compound of the formula I is preferably used in the form of its racemate.
  • the metallocene compound is preferably used in a concentration, based on the transition metal, of 10 -3 to 10 -8 , preferably 10 -4 to 10 -7 mol, transition metal per dm 3 reactor volume.
  • the aluminoxane is used in a concentration of 10 -4 to 10 -1 , preferably 10 -4 to 2 * 10 -2 mol per dm 3 reactor volume, based on the aluminum content. In principle, however, higher concentrations are also possible.
  • At least one cyclic, preferably polycyclic, olefin is polymerized with at least one acyclic olefin.
  • Polycyclic olefins preferably have the formulas VI, VII, VIII, IX, X or XI , wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are the same or different and a hydrogen atom or a C 1 -C 20 hydrocarbon radical such as C 1 -C 8 alkyl or C 6 -C 10 aryl, or two or more radicals R 7 -R 14 together form a C 4 -C 40 ring system, the same radicals R 7 -R 14 having different meanings in the different formulas.
  • Cycloolefins of the formulas VI or VIII in which R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are identical or different and a hydrogen atom or a C 1 -C 20 hydrocarbon radical are particularly preferred , in particular a C 6 -C 10 aryl radical or a C 1 -C 8 alkyl radical, the same radicals R 7 -R 14 in the different formulas VI-XI having different meanings.
  • Acyclic olefins are preferably 1-olefins having 1 to 40, preferably 1 to 20, carbon atoms.
  • 1-olefins of the formula (XII) are particularly preferred wherein R 15 , R 16 , R 17 and R 18 are the same or different and represent a hydrogen atom or a C 1 -C 20 hydrocarbon radical, preferably a C 6 -C 10 aryl radical and a C 1 -C 8 alkyl radical.
  • Examples of acyclic olefins are ethylene and propylene.
  • one or more monocyclic olefins in particular of the formula (XIII), are also used in the process according to the invention where n is a number from 2 to 10.
  • copolymers of polycyclic olefins are preferred of the formulas VI and VIII, produced with ethylene.
  • Particularly preferred polycyclic olefins are norbornene and tetracyclododecene, which may be substituted by (C 1 -C 6 ) alkyl. They are preferably copolymerized with ethylene; ethylene / norbornene copolymers are particularly important.
  • the polycyclic olefin is preferred in the process according to the invention in an amount of 0.1 to 99.9 wt .-%, the monocyclic olefin in one Amount from 0 to 99.9% by weight, and the acyclic olefin in an amount of 0.1 to 99.9% by weight, based in each case on the total amount of the monomers, used.
  • the concentration of the acyclic olefin used results from this Solubility in the reaction medium at given pressure and given Temperature.
  • polycyclic olefins monocyclic olefins and acyclic olefins are to understand mixtures of two or more olefins of the respective type. This means that in addition to polycyclic bicopolymers, ter- and Multicopolymers can be produced by the process according to the invention. Copolymers of monocyclic olefins and acyclic olefins can also the method according to the invention can be obtained.
  • cyclopentene which can be substituted, is prefers.
  • the process according to the invention is preferred at temperatures from -78 to 150 ° C, especially 0 to 100 ° C, and a pressure of 0.01 to 64 bar carried out.
  • the polymerization is carried out in the liquid cycloolefin itself or in cycloolefin solution carried out, wherein the pressure is advantageously above 1 bar.
  • the variation of the molar ratios can of the polycyclic olefin to the open-chain olefin used in one wide range. Molar ratios of 3: 1 to are preferred 100: 1 cycloolefin used to open-chain olefin.
  • Molar ratios of 3: 1 to are preferred 100: 1 cycloolefin used to open-chain olefin.
  • the polymerization can also be carried out in several stages, including block copolymers can arise (EP-A-560 090).
  • the average molecular weight of the polymer formed can be further determined Hydrogen dosing, variation of the catalyst concentration or variation control the temperature in a known manner.
  • the polydispersity M w / M n of the cycloolefin copolymers is quite narrow with values from 1.9 to 3.5. This results in a property profile that makes them particularly suitable for injection molding.
  • the process according to the invention can be used to produce amorphous cycloolefin copolymers produce that do not contain semi-crystalline ethylene polymers.
  • the copolymers are transparent, hard and thermoplastically processable.
  • the Tensile stresses (according to DIN 53457) are in the range of 50 to 100 MPa, preferably between 55 and 70 MPa. Both when extruding and when Injection molding did not cause decomposition reactions at temperatures of 300 ° C or found a viscosity reduction.
  • the cycloolefin copolymers produced according to the invention are particularly suitable for the production of moldings such as extrusion parts (for example films, tubes, tubes, rods and fibers) or injection molded articles of any shape and size.
  • the films can be extruded films, calendered films, cast films, mono- and biaxially oriented films or multilayer films and are particularly suitable as food packaging films or blister packs. They have a high water barrier effect and low gas permeability.
  • cycloolefin copolymers prepared according to the invention are also suitable as Additive in other polymer films (especially polyolefin films such as Polypropylene films or polyethylene films) e.g. for the purpose of Flow improvement, improvement of paintability, modulus of elasticity and Manufacture of opaque films.
  • Cycloolefin copolymers are their transparency. This is especially the reason optical applications of the extruded or injection molded parts Cycloolefin copolymers are of great importance.
  • the one with an Abbe refractometer and mixed light determined refractive index of the in the The reaction products described in the following examples are in the range between 1.520 and 1.555.
  • the products according to the invention can be used as Glass substitutes find various applications such as lenses, Prisms, carrier plates and foils for optical data storage, for video plates, for compact discs, as cover and focusing disks for solar cells, as cover and Diffusers for power optics, as optical fibers in the form of Fibers or foils.
  • the cycloolefin copolymers obtained according to the invention are also suitable for Production of polymer alloys can be used.
  • the alloys can be used in the Melt or be made in solution.
  • the alloys each have a combination of properties that is favorable for certain applications Components.
  • the following polymers can preferably be used as cycloolefin copolymers: Polyethylene, polypropylene, (ethylene-propylene) copolymers, polybutylene, PVC (4-methyl-1-pentene), Polyisoprene, polyisobutylene, natural rubber, poly (methyl methacrylate), further polymethacrylates, polyacrylates, (acrylate methacrylate) copolymers, Polystyrene, (styrene-acrylonitrile) copolymers, bisphenol-A polycarbonate, other polycarbonates, aromatic polyester carbonates, Polyethylene terephthalate, polybutylene terephthalate, amorphous polyarylates, nylon-6, Nylon-66, other polyamides, polyaramides, polyether ketones, polyoxymethylene, Polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, Polyvinylidene fluoride.
  • the method according to the invention delivers with high activity in particular transparent cycloolefin copolymers that have high tear strengths.
  • the glass transition temperatures given in the following examples were Tg by means of DSC (Differential Scanning Calorimetry) at a heating rate of 20 ° C / min determined.
  • the indicated viscosity numbers were according to DIN 53728 determined.
  • the mechanical properties were in Tensile elongation test measured (DIN 53457, Instron 4302).
  • the Al / CH 3 ratio in the aluminoxane was determined by decomposing the sample with H 2 SO 4 and determining the volume of the hydrolysis gases formed under normal conditions, and by complexometric titration of the aluminum in the then dissolved sample according to Schwarzenbach.
  • the compounds were characterized by 1 H-NMR, 13 C-NMR and IR spectroscopy.
  • a solution of the zirconium amide (416 mg, 1.55 mmol) in 25 ml of toluene is cooled to -78 ° C. and then a solution of 345 mg of the ligand in 10 ml of toluene is added dropwise.
  • the solution is warmed to room temperature and, after stirring for 12 hours, heated to 80 ° C. for 3 hours.
  • the solvent is removed in vacuo and the complex is obtained in the form of a yellow-orange solid in 99% yield (613 mg).
  • a solution of the hafnium amide (833 mg, 1.55 mmol) in 25 ml of xylene is cooled to -78 ° C. and then a solution of 522 mg of the ligand in 10 ml of xylene is added dropwise.
  • the solution is warmed to room temperature and, after stirring for 2 hours, heated to 150 ° C. for 8 hours.
  • the solvent is removed in vacuo and the complex is recrystallized from a little pentane.
  • the complex precipitates in the form of a yellow-orange solid (95% yield, 613 mg).
  • 600 cm 3 of an 85% strength by weight solution of norbornene in toluene are placed in a 1.5 dm 3 autoclave which has been thoroughly rinsed with ethene beforehand. The solution was saturated with ethene by pressing ethene (6 bar) several times. 5 cm 3 of toluene methylaluminoxane solution (10.1% by weight methylaluminoxane solution with a molecular weight of 1300 g / mol after cryoscopic determination) were metered in countercurrent into the reactor thus prepared and stirred at 70 ° C. for 30 minutes.
  • the mixture was polymerized at 70 ° C. for one hour with stirring (750 rpm), the Ethene pressure was kept at 6 bar by metering.
  • the polymerization mixture was drained into a vessel and immediately introduced into 5 dm 3 of acetone, stirred for 10 minutes and then the precipitated product was filtered.
  • the filter cake was washed three times alternately with 10% hydrochloric acid and acetone. Finally, it was washed neutral with water, the residue was slurried in acetone and filtered again.
  • the polymer purified in this way was dried at 80 ° C. in vacuo (0.2 bar) for 15 hours.
  • Example A was repeated at an ethylene pressure of 18 bar and a polymerisation temperature of 90 ° C.
  • the yield of purified and dried polymer was 152 g.
  • the polymer had a glass transition temperature of 150 ° C., a viscosity number of 70 cm 3 / g, a tensile strength at break of 62 MPa and an elongation at break of 3.5%.
  • the activity A * was 56182 g polymer / hx mmol.
  • Example B The procedure was as in Example B, but 0.5 mg of isopropylidene-bis (1-indenyl) bis (N, N-dimethylamido) zirconium (II) were used as metallocene. 114 g of purified and dried polymer were obtained, with a glass transition temperature of 143 ° C. and a viscosity number of 152 cm 3 / g.
  • Example A The procedure was as in Example A, but the metallocene used was 0.1 mg of dimethylsilanediyl- (9- (2,7-di-tert-butyl) fluorenyl) cyclopentadienyl-bis (N, N-dimethylamido) zirconium (III) , 17 g of purified and dried polymer were obtained with a glass transition temperature of 143 ° C. and a viscosity number of 267 cm 3 / g.
  • Example A The procedure was as in Example A, but 0.2 mg of isopropylidene (9-fluorenyl) cyclopentadienyl-bis (N, N-dimethylamido) zirconium (IV) was used as the metallocene. 64 g of purified and dried polymer were obtained, with a glass transition temperature of 151 ° C. and a viscosity number of 147 cm 3 / g.

Description

Die vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung eines Cycloolefincopolymeren in Gegenwart einer Metallocenverbindung.The present invention relates to a method for producing a Cycloolefin copolymers in the presence of a metallocene compound.

Metallocenverbindungen der 4. Nebengruppe des Periodensystems der Elemente sind in Kombination mit Methylaluminoxan (MAO) aktive Katalysatoren für die Polymerisation von Olefinen. Aus der Literatur ist die Herstellung von Polyolefinen mit löslichen Metallocenverbindungen in Kombination mit Aluminoxanen oder anderen Cokatalysatoren, die aufgrund ihrer Lewis-Acidität das neutrale Metallocen in eine Kation überführen und stabilisieren können, bekannt (EP-A-129 368).Metallocene compounds of subgroup 4 of the periodic table of the Elements are active in combination with methylaluminoxane (MAO) Catalysts for the polymerization of olefins. It is from the literature Production of polyolefins with soluble metallocene compounds in Combination with aluminoxanes or other cocatalysts due to their Lewis acidity convert the neutral metallocene into a cation and can stabilize, known (EP-A-129 368).

Metallocene und Halbsandwichkomplexe sind nicht nur hinsichtlich der Polymerisation oder Oligomerisation von Olefinen von großem Interesse. Sie können auch als Hydrier-, Epoxidations-, Isomerisierungs-, C-C-Kupplungskatalysatoren eingesetzt werden (Chem. Rev. 1992, 92, 965-994).Metallocenes and half-sandwich complexes are not just about Polymerization or oligomerization of olefins of great interest. she can also be used as hydrogenation, epoxidation, isomerization, C-C coupling catalysts are used (Chem. Rev. 1992, 92, 965-994).

Aus der Literatur ist bekannt, daß man CpH mit Zirkonium- oder Hafniumdimethyltetraamid direkt und ohne Zusatz einer Base zu Metallocenen der in EP-A-595 390 und EP-A-283 164 beschriebenen Typen umsetzen kann (J. Chem. Soc. (A), 1968, 1940-1945). Weiterhin ist bekannt, Cycloolefincopolymere in Gegenwart verbrückter Metallocene herzustellen (EP-A-283 164, EP-A-407 870). It is known from the literature that CpH with zirconium or Hafniumdimethyltetraamide directly and without adding a base to metallocenes which can implement the types described in EP-A-595 390 and EP-A-283 164 (J. Chem. Soc. (A), 1968, 1940-1945). It is also known To produce cycloolefin copolymers in the presence of bridged metallocenes (EP-A-283 164, EP-A-407 870).

EP 0659758 bezieht sich auf eine stereorigide Metallocenverbindung, die als Liganden mindestens zwei substituierte oder unsubstituierte Cyclopendadienylgruppen aufweist, die über ein mono- oder polycyclisches Ringsystem miteinander verbunden sind, wobei mindestens eine Cyclopentadienylgruppe an das mono- oder polycyclische Ringsystem anelliert ist und ein Verfahren zur Herstellung eines Cycloolefincopolymers. Die so erhaltenen Cycloolefincopolymere weisen hohe Reißfestigkeiten auf und eignen sich zur Herstellung von Extrusionsteilen und Spritzgußartikeln.EP 0659758 relates to a stereorigid metallocene compound, which as Ligands at least two substituted or unsubstituted Cyclopendadienyl groups has a mono- or polycyclic Ring system are interconnected, at least one Cyclopentadienyl group on the mono- or polycyclic ring system is fused and a process for the preparation of a cycloolefin copolymer. The cycloolefin copolymers obtained in this way have high tear strengths and are suitable for the production of extrusion parts and injection molded articles.

Es bestand die Aufgabe, ein wirtschaftliches Verfahren zur Herstellung von Cycloolefincopolymeren zur Verfügung zu stellen. Diese Aufgabe wird durch die vorliegende Erfindung gelöst. The task was to develop an economical process for the production of To provide cycloolefin copolymers. This task is accomplished by solved the present invention.

Die vorliegende Erfindung betrifft somit ein Verfahren zur Herstellung eines Cycloolefincopolymeren durch Polymerisation mindestens eines cyclischen Olefins und mindestens eines acyclischen Olefins, in Gegenwart eines Katalysators enthaltend mindestens eine Metallocenverbindung der Formel I,

Figure 00030001
   worin L und L' eine substituierte oder unsubstituierte Cyclopentadienylgruppe ist, T eine Verbrückung zwischen L und L' ist, und [R5R6X]n bedeutet, worin X unabhängig voneinander gleich oder verschieden Kohlenstoff, Silizium, Germanium oder Zinn sind, die Reste R5 und R6 unabhängig voneinander ein Wasserstoffatom oder einen C1-C30-Kohlenwasserstoffrest bedeuten, und n gleich 1, 2, 3 oder 4 bedeutet, M ein vierwertiges Übergangsmetall ist, und R1, R2, R3 und R4 unabhängig voneinander gleich oder verschieden ein Wasserstoffatom oder ein C1-C20-Kohlenwasserstoffrest ist.The present invention thus relates to a process for the preparation of a cycloolefin copolymer by polymerizing at least one cyclic olefin and at least one acyclic olefin, in the presence of a catalyst comprising at least one metallocene compound of the formula I,
Figure 00030001
wherein L and L 'is a substituted or unsubstituted cyclopentadienyl group, T is a bridge between L and L', and means [R 5 R 6 X] n , where X is independently the same or different carbon, silicon, germanium or tin, which R 5 and R 6 independently represent a hydrogen atom or a C 1 -C 30 hydrocarbon radical, and n represents 1, 2, 3 or 4, M is a tetravalent transition metal, and R 1 , R 2 , R 3 and R 4 independently of one another, the same or different, is a hydrogen atom or a C 1 -C 20 hydrocarbon radical.

M ist gleich Titan, Zirkonium oder Hafnium. Vorteilhaft bedeuten R5 und R6 ein Wasserstoffatom, C1-C20-Alkyl oder C6-C20-Aryl, und n ist bevorzugt 1 oder 2. Für n = 2 bedeutet T bevorzugt Kohlenstoff, Silizium, Germanium oder Zinn.M is titanium, zirconium or hafnium. R 5 and R 6 advantageously denote a hydrogen atom, C 1 -C 20 alkyl or C 6 -C 20 aryl, and n is preferably 1 or 2. For n = 2, T preferably denotes carbon, silicon, germanium or tin.

R1 und R3 sind unabhängig voneinander gleich oder verschieden ein Wasserstoffatom oder ein C1-C20-Kohlenwasserstoffrest, bevorzugt ein C1-C20-Kohlenwasserstoffrest wie C1-C20-Alkyl oder C6-C14-Aryl, insbesondere Methyl.R 1 and R 3 are, independently of one another, identical or different, a hydrogen atom or a C 1 -C 20 hydrocarbon radical, preferably a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 14 aryl, in particular Methyl.

R2 und R4 sind unabhängig voneinander gleich oder verschieden und bevorzugt ein C1-C20-Kohlenwasserstoffrest wie C1-C20-Alkyl oder C6-C14-Aryl, insbesondere Methyl.R 2 and R 4 are independently the same or different and preferably a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 14 aryl, especially methyl.

Die Reste R1, R2, R3 und R4 sind unabhängig voneinander gleich oder verschieden. Bevorzugt sind die Reste R1, R2, R3 und R4 gleich und ein C1-C20-Alkyl oder C6-C14-Aryl, insbesondere Methyl.The radicals R 1 , R 2 , R 3 and R 4 are independently the same or different. The radicals R 1 , R 2 , R 3 and R 4 are preferably identical and are a C 1 -C 20 alkyl or C 6 -C 14 aryl, in particular methyl.

Beispiele für substituierte Cyclopentadienylgruppen L oder L' sind:

  • Tetramethylcyclopentadienyl, Methylcyclopentadienyl,
  • Methyl-tert.-butylcyclopentadienyl, Tert.-butylcyclopentadienyl,
  • Isopropylcyclopentadienyl, Dimethylcyclopentadienyl,
  • Trimethylcyclopentadienyl, Trimethylethylcyclopentadienyl,
  • Phenylcyclopentadienyl, Diphenylcyclopentadienyl, Indenyl, 2-Methylindenyl,
  • 2-Ethylindenyl, 3-Methylindenyl, 3-tert.-butylindenyl, 3-Trimethylsilylindenyl,
  • 2-Methyl-4-phenylindenyl, 2-Ethyl-4-phenylindenyl,
  • 2-Methyl-4-naphthyl-indenyl, 2-Methyl-4-isopropyl-indenyl, 4,5-Benzoindenyl,
  • 2-Methyl-4,5-benzoindenyl, 2-Methyl-α-acenaphthindenyl,
  • 2-Methyl-4,6-diisopropylindenyl, Fluorenyl, 4-Methylfluorenyl oder
  • 2,7-Di-tert.-butylfluorenyl.
    • Examples of substituted cyclopentadienyl groups L or L 'are:
  • Tetramethylcyclopentadienyl, methylcyclopentadienyl,
  • Methyl tert-butylcyclopentadienyl, tert-butylcyclopentadienyl,
  • Isopropylcyclopentadienyl, dimethylcyclopentadienyl,
  • Trimethylcyclopentadienyl, trimethylethylcyclopentadienyl,
  • Phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl,
  • 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl,
  • 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl,
  • 2-methyl-4-naphthyl-indenyl, 2-methyl-4-isopropyl-indenyl, 4,5-benzoindenyl,
  • 2-methyl-4,5-benzoindenyl, 2-methyl-α-acenaphthindenyl,
  • 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or
  • 2,7-di-tert-butylfluorenyl.

    • Beispiele für Verbrückungen T sind:

  • Dimethylsilandiyl, Methylphenylsilandiyl, Diphenylsilandiyl, Dimethylgermandiyl,
  • 1,2-Tetramethyldisilandiyl, 1,2-Ethyliden, 1,2-Propyliden, 1,2-Butyliden,
  • 1,3-Propyliden, 1,4-Butyliden oder 2,2-Propyliden.
    • Examples of bridges T are:
  • Dimethylsilanediyl, methylphenylsilanediyl, diphenylsilanediyl, dimethylgermanediyl,
  • 1,2-tetramethyldisilanediyl, 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene,
  • 1,3-propylidene, 1,4-butylidene or 2,2-propylidene.

    • Beispiele für Metallocenverbindungen der Formel I sind:

  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propyliden)}-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propyliden)]-hafnium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(fluorenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(fluorenyl)propyliden)]-hafnium
  • Bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(indenyl)propyliden)]-hafnium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(fluorenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(2-methyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:ηh5-2,2-(tetramethylcyclopentadienyl)(indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(2-ethyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(2-methyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(2-ethyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(3-trimethylsilyl-indenyl)-propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-methyl-indenyl)-propylinden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-ethyl-indenyl)-propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(3-trimethylsilyl-indenyl)-propyliden)]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-(cyclopentadienyl)(indenyl)]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-(cyclopentadienyl)(indenyl)]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-(fluorenyl)(indenyl)]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(methylcyclopentadienyl) (indenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(methylcyclopentadienyl)(fluorenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(fluorenyl)(2-methyl-indenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(tetramethylcyclopentadienyl)(indenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(tetramethylcyclopentadienyl)(fluorenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(fluorenyl)(2-ethyl-indenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(cyclopentadienyl)(2-methylindenyl))]-zirkunium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(cyclopentadienyl)(2-ethylindenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(cyclopentadienyl)(3-trimethylsilyl-indenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(methylcyclopentadienyl)(2-methyl-indenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(methylcyclopentadienyl)(2-ethylindenyl))]-zirkonium
  • Bis(dimethylamido)[dimethylsilandiyl(η5:η5-2,2-(methylcyclopentadienyl)(3-trimethylsilyl-indenyl))]-zirkonium
  • Stantetraylbis[(η5:η5-bis(cyclopentadienyl)]zirkoniumbis(dimethylamido)
    • Examples of metallocene compounds of the formula I are:
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (indenyl) propylidene)} - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (indenyl) propylidene)] - hafnium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (fluorenyl) propylidene]] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (fluorenyl) propylidene)] - hafnium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (fluorenyl) (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (fluorenyl) (indenyl) propylidene)] - hafnium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (fluorenyl) propylidene]] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (fluorenyl) (2-methyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : ηh 5 -2,2- (tetramethylcyclopentadienyl) (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (tetramethylcyclopentadienyl) (fluorenyl) propylidene]] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (fluorenyl) (2-ethyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (2-methyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (2-ethyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (3-trimethylsilyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (2-methyl-indenyl) propylinden)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (2-ethyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (3-trimethylsilyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 - (cyclopentadienyl) (indenyl)] - zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 - (cyclopentadienyl) (indenyl)] - zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 - (fluorenyl) (indenyl)] - zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (methylcyclopentadienyl) (indenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (methylcyclopentadienyl) (fluorenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (fluorenyl) (2-methyl-indenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (tetramethylcyclopentadienyl) (indenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (tetramethylcyclopentadienyl) (fluorenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (fluorenyl) (2-ethyl-indenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (cyclopentadienyl) (2-methylindenyl))] zirkunium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (cyclopentadienyl) (2-ethylindenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (cyclopentadienyl) (3-trimethylsilyl-indenyl))) zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (methylcyclopentadienyl) (2-methyl-indenyl))) zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (methylcyclopentadienyl) (2-ethylindenyl))] zirconium
  • Bis (dimethylamido) [dimethylsilanediyl (η 5 : η 5 -2,2- (methylcyclopentadienyl) (3-trimethylsilyl-indenyl))) zirconium
  • Stantetraylbis [(η 5 : η 5 -bis (cyclopentadienyl)] zirconium bis (dimethylamido)

    • Als bevorzugte Form der Metallocenverbindung der Formel (I) wird in dem erfindungsgemäßen Verfahren eine Metallocenverbindung der Formel (II) eingesetzt erfindungsgemäßen Verfahren eine Metallocenverbindung der Formel (II) eingesetzt

    Figure 00070001
    worin Cp eine unsubstituierte oder substituierte Cyclopentadienylgruppe bedeutet, Ind unsubstituiertes oder substituiertes Indenyl bedeutet, M ein vierwertiges Übergangsmetall bedeutet, R1, R2, R3 und R4 unabhängig voneinander gleich oder verschieden sind und ein Wasserstoffatom oder ein C1-C20-Kohlenwasserstoffrest bedeuten, R5 und R6 unabhängig voneinander gleich oder verschieden sind und ein Wasserstoffatom oder einen C1-C30-Kohlenwasserstoffrest bedeuten.As a preferred form of the metallocene compound of the formula (I), a metallocene compound of the formula (II) is used in the process according to the invention, and a metallocene compound of the formula (II) is used according to the process of the invention
    Figure 00070001
    wherein Cp denotes an unsubstituted or substituted cyclopentadienyl group, Ind denotes unsubstituted or substituted indenyl, M denotes a tetravalent transition metal, R 1 , R 2 , R 3 and R 4 are independently the same or different and a hydrogen atom or a C 1 -C 20 - Are hydrocarbon radical, R 5 and R 6 are independently the same or different and represent a hydrogen atom or a C 1 -C 30 hydrocarbon radical.

    In Formel II ist M gleich Titan, Zirkonium oder Hafnium.In Formula II, M is titanium, Zirconium or hafnium.

    Cp ist eine unsubstituierte oder substituierte Cyclopentadienylgruppe. Beispiele für substituierte Cyclopentadienylgruppen Cp sind:

  • Tetramethylcyclopentadienyl, Methylcyclopentadienyl,
  • Methyl-tert.-butylcyclopentadienyl, Tert.-butylcyclopentadienyl,
  • Isopropylcyclopentadienyl, Dimethylcyclopentadienyl,
  • Trimethylcyclopentadienyl, Trimethylethylcyclopentadienyl,
  • Phenylcyclopentadienyl, Diphenylcyclopentadienyl, Indenyl, 2-Methylindenyl,
  • 2-Ethylindenyl, 3-Methylindenyl, 3-tert.-butylindenyl, 3-Trimethylsilylindenyl,
  • 2-Methyl-4-phenylindenyl, 2-Ethyl-4-phenylindenyl,
  • 2-Methyl-4,6-diisopropylindenyl, Fluorenyl, 4-Methylfluorenyl oder
  • 2,7-Di-tert.-butylfluorenyl.
    • Cp is an unsubstituted or substituted cyclopentadienyl group. Examples of substituted cyclopentadienyl groups Cp are:
  • Tetramethylcyclopentadienyl, methylcyclopentadienyl,
  • Methyl tert-butylcyclopentadienyl, tert-butylcyclopentadienyl,
  • Isopropylcyclopentadienyl, dimethylcyclopentadienyl,
  • Trimethylcyclopentadienyl, trimethylethylcyclopentadienyl,
  • Phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl,
  • 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl,
  • 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl,
  • 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or
  • 2,7-di-tert-butylfluorenyl.

    • Ind ist unsubstituiertes oder substituiertes Indenyl. Beispiele für substituiertes Indenyl sind: 2-Methylindenyl, 2-Ethylindenyl, 3-Methylindenyl, 3-tert.-butylindenyl, 3-Trimethylsilylindenyl, 2-Methyl-4-phenylindenyl, 2-Ethyl-4-phenylindenyl, 2-Methyl-4-naphthyl-indenyl, 2-Methyl-4-isopropyl-indenyl, 4,5-benzoindenyl, 2-Methyl-4,5-benzoindenyl, 2-Methyl-α-acenaphthindenyl, 2-Methyl-4,6-diisopropylindenyl. Bevorzugt bedeutet Ind unsubstituiertes Indenyl.Ind is unsubstituted or substituted indenyl. Examples of substituted Indenyl are: 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthyl-indenyl, 2-methyl-4-isopropyl-indenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-α-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl. Prefers means Ind unsubstituted indenyl.

    Die Reste R5 und R6 sind unabhängig voneinander gleich oder verschieden, bevorzugt gleich, und ein Wasserstoffatom oder ein C1-C30-Kohlenwasserstoffrest wie C1-C20-Alkyl oder C6-C20-Aryl. Bevorzugt sind R5 und R6 Methyl oder Phenyl, insbesondere Methyl.The radicals R 5 and R 6 are, independently of one another, identical or different, preferably identical, and a hydrogen atom or a C 1 -C 30 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 20 aryl. R 5 and R 6 are preferably methyl or phenyl, in particular methyl.

    R1 und R3 sind unabhängig voneinander gleich oder verschieden ein Wasserstoffatom oder ein C1-C20-Kohlenwasserstoffrest, bevorzugt ein C1-C20-Kohlenwasserstoffrest, wie C1-C20-Alkyl oder C6-C14-Aryl, insbesondere Methyl.R 1 and R 3 are, independently of one another, identical or different, a hydrogen atom or a C 1 -C 20 hydrocarbon radical, preferably a C 1 -C 20 hydrocarbon radical, such as C 1 -C 20 alkyl or C 6 -C 14 aryl, especially methyl.

    R2 und R4 sind unabhängig voneinander gleich oder verschieden und bevorzugt ein C1-C20-Kohlenwasserstoffrest wie C1-C20-Alkyl oder C6-C14-Aryl, insbesondere Methyl.R 2 and R 4 are independently the same or different and preferably a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or C 6 -C 14 aryl, especially methyl.

    Die Reste R1, R2, R3 und R4 sind unabhängig voneinander gleich oder verschieden. Bevorzugt sind die Reste R1, R2, R3 und R4 gleich und ein C1-C20-Kohlenwasserstoffrest wie C1-C20-Alkyl ode rC6-C14-Aryl, insbesondere Methyl.The radicals R 1 , R 2 , R 3 and R 4 are independently the same or different. The radicals R 1 , R 2 , R 3 and R 4 are preferably the same and a C 1 -C 20 hydrocarbon radical such as C 1 -C 20 alkyl or rC 6 -C 14 aryl, in particular methyl.

    Beispiele für Metallocenverbindungen der Formel II sind:

  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propyliden)]-hafnium
  • Bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(indenyl)propyliden)]-hafnium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)(η5:η5-2,2-(fluorenyl)(2-methyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:ηh5-2,2-(tetramethylcyclopentadienyl)(indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(2-ethyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(2-methyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(2-ethyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)(η5:η5-2,2-(cyclopentadienyl)(3-trimethylsilyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-methyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-ethyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(3-trimethylsilyl-indenyl)propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-(2-methyl-indenyl)-(indenyl)-propyliden)]-zirkonium
  • Bis(dimethylamido)[η5:η5-2,2-bis(indenyl)-propyliden)]-zirkonium.
    • Examples of metallocene compounds of the formula II are:
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (indenyl) propylidene)] - hafnium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (fluorenyl) (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (fluorenyl) (indenyl) propylidene)] - hafnium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) (η 5 : η 5 -2,2- (fluorenyl) (2-methyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : ηh 5 -2,2- (tetramethylcyclopentadienyl) (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (fluorenyl) (2-ethyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (2-methyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (2-ethyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) (η 5 : η 5 -2,2- (cyclopentadienyl) (3-trimethylsilyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (2-methyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (2-ethyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (methylcyclopentadienyl) (3-trimethylsilyl-indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2- (2-methyl-indenyl) - (indenyl) propylidene)] - zirconium
  • Bis (dimethylamido) [η 5 : η 5 -2,2-bis (indenyl) propylidene]] - zirconium.

    • Die Metallocenverbindung der Formel I oder II kann hergestellt werden durch Umsetzung einer Verbindung der Formel III, worin L ein π-Ligand, L' ein π-Ligand, T eine Verbrückung und m gleich 1 oder 2 ist, mit einer Verbindung der Formel IV, worin M ein vierwertiges Metall ist, und R1, R2, R3 und R4 unabhängig voneinander gleich oder verschieden ein Wasserstoffatom oder einen C1-C20-Kohlenwasserstoffrest bedeuten

    Figure 00100001
    The metallocene compound of the formula I or II can be prepared by reacting a compound of the formula III, in which L is a π ligand, L 'is a π ligand, T is a bridge and m is 1 or 2, with a compound of the formula IV, wherein M is a tetravalent metal, and R 1 , R 2 , R 3 and R 4 independently of one another are identical or different and represent a hydrogen atom or a C 1 -C 20 hydrocarbon radical
    Figure 00100001

    Die Reaktion wird bevorzugt in einem aprotischen Lösungsmittel, z.B. Toluol oder Hexan durchgeführt. Die Temperatur kann zwischen -78 und 140°C betragen, bevorzugt 0°C bis 110°C. Die Verbindung der Formel III kann im Überschuß eingesetzt werden, bevorzugt werden 1 Äquivalent der Verbindung der Formel III und 1 Äquivalent des Metalltetramids der Formel IV verwendet.The reaction is preferably carried out in an aprotic solvent, e.g. toluene or hexane. The temperature can be between -78 and 140 ° C amount, preferably 0 ° C to 110 ° C. The compound of formula III can Excess are used, 1 equivalent of the compound are preferred of the formula III and 1 equivalent of the metal tetramide of the formula IV used.

    Verfahren zur Herstellung von Verbindungen der allgemeinen Formel III sind bekannt (Chem. Ber. 1990, 123, 1649-1651). Verfahren zur Herstellung von Verbindungen der allgemeinen Formel IV sind ebenfalls bekannt (J. Chem. Soc. 1960, 3857-3861).Processes for the preparation of compounds of general formula III are known (Chem. Ber. 1990, 123, 1649-1651). Process for the production of Compounds of the general formula IV are also known (J. Chem. Soc. 1960, 3857-3861).

    Bevorzugt wird in dem erfindungsgemäßen Verfahren ein Katalysator eingesetzt, der mindestens eine Metallocenverbindung der Formel I und mindestens einen Cokatalysator enthält. Es können auch Mischungen von zwei oder mehr Metallocenverbindungen verwendet werden, insbesondere zur Herstellung von Reaktorblends oder von Cycloolefincopolymeren mit breiter oder multimodaler Molmassenverteilung.A catalyst is preferably used in the process according to the invention, the at least one metallocene compound of the formula I and at least one Contains cocatalyst. Mixtures of two or more can also be used Metallocene compounds are used, in particular for the production of Reactor blends or of cycloolefin copolymers with broad or multimodal Molecular weight distribution.

    Prinzipiell ist als Cokatalysator in dem erfindungsgemäßen Verfahren jede Verbindung geeignet, die aufgrund ihrer Lewis-Acidität die neutrale Metallocenverbindung in ein Kation überführen und dieses stabilisieren kann ("labile Koordination"). Darüber hinaus soll der Cokatalysator oder das aus ihm gebildete Anion keine weiteren Reaktionen mit dem gebildeten Kation eingehen (EP-A-427 697). Als Cokatalysator wird bevorzugt eine Aluminiumverbindung und/oder eine Borverbindung verwendet.In principle, each is a cocatalyst in the process according to the invention Compound suitable because of its Lewis acidity the neutral Can convert metallocene compound into a cation and stabilize it ("unstable coordination"). In addition, the cocatalyst, or that of it formed anion do not undergo any further reactions with the cation formed (EP-A-427 697). An aluminum compound is preferred as the cocatalyst and / or a boron compound is used.

    Die Borverbindung hat bevorzugt die Formel Ra xNH4-xBRb 4, Ra xPH4-xBRb 4, Ra 3CBRb 4 oder BRb 3, worin x eine Zahl von 1 bis 4, bevorzugt 3, bedeutet, die Reste Ra gleich oder verschieden, bevorzugt gleich sind, und C1-C10-Alkyl oder C6-C18-Aryl sind, oder zwei Reste Ra zusammen mit dem sie verbindenden Atomen einen Ring bilden, und die Reste Rb gleich oder verschieden, bevorzugt gleich sind, und C6-C18-Aryl sind, das durch Alkyl, Haloalkyl oder Fluor substituiert sein kann. Insbesondere steht Ra für Ethyl, Propyl, Butyl oder Phenyl und Rb für Phenyl, Pentafluorphenyl, 3,5-Bistrifluormethylphenyl, Mesityl, Xylyl oder Tolyl (EP-A-277 003, EP-A-277 004 und EP-A-426 638).The boron compound preferably has the formula R a x NH 4-x BR b 4 , R a x PH 4-x BR b 4 , R a 3 CBR b 4 or BR b 3 , where x is a number from 1 to 4, preferably 3 , means the radicals R a are the same or different, preferably the same, and are C 1 -C 10 alkyl or C 6 -C 18 aryl, or two radicals R a together with the atoms connecting them form a ring, and the R b radicals are the same or different, preferably the same, and are C 6 -C 18 aryl, which can be substituted by alkyl, haloalkyl or fluorine. In particular, R a is ethyl, propyl, butyl or phenyl and R b is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP-A-277 003, EP-A-277 004 and EP-A- 426 638).

    Bevorzugt wird als Cokatalysator eine Aluminiumverbindung wie Aluminoxan und/oder ein Aluminiumalkyl eingesetzt.An aluminum compound such as aluminoxane is preferred as the cocatalyst and / or an aluminum alkyl used.

    Besonders bevorzugt wird als Cokatalysator ein Aluminoxan, insbesondere der Formel Va für den linearen Typ und/oder der Formel Vb für den cyclischen Typ verwendet,

    Figure 00110001
    Figure 00120001
    wobei in den Formeln Va und Vb die Reste Rc gleich oder verschieden sind und Wasserstoff oder eine C1-C20-Kohlenwasserstoffgruppe wie eine C1-C18-Alkylgruppe, eine C6-C18-Arylgruppe oder Benzyl bedeuten und p eine ganze Zahl von 2 bis 50, bevorzugt 10 bis 35 bedeutet.An aluminoxane, in particular of the formula Va for the linear type and / or of the formula Vb for the cyclic type, is particularly preferably used as cocatalyst,
    Figure 00110001
    Figure 00120001
    where in the formulas Va and Vb the radicals R c are identical or different and are hydrogen or a C 1 -C 20 hydrocarbon group such as a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group or benzyl and p is a is an integer from 2 to 50, preferably 10 to 35.

    Bevorzugt sind die Reste Rc gleich und bedeuten Wasserstoff, Methyl, Isobutyl, Phenyl oder Benzyl, besonders bevorzugt Methyl.The radicals R c are preferably the same and are hydrogen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl.

    Sind die Reste Rc verschieden, so sind sie bevorzugt Methyl und Wasserstoff oder alternativ Methyl und Isobutyl, wobei Wasserstoff oder Isobutyl bevorzugt in einem zahlenmäßigen Anteil von 0,01 bis 40 % (der Reste Rc) enthalten sind.If the radicals R c are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in a proportion of from 0.01 to 40% (of the radicals R c ).

    Die Verfahren zur Herstellung der Aluminoxane sind bekannt. Die genaue räumliche Struktur der Aluminoxane ist nicht bekannt (J. Am. Chem. Soc. (1993) 115, 4971). Beispielsweise ist denkbar, daß sich Ketten und Ringe zu größeren zweidimensionalen oder dreidimensionalen Strukturen verbinden.The processes for producing the aluminoxanes are known. The exact spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is conceivable that chains and rings become closed connect larger two-dimensional or three-dimensional structures.

    Unabhängig von der Art der Herstellung ist allen Aluminoxanlösungen ein wechselnder Gehalt an nicht umgesetzter Aluminiumausgangsverbindung, die in freier Form oder als Addukt vorliegt, gemeinsam.Regardless of the type of manufacture, all aluminoxane solutions are one changing content of unreacted aluminum starting compound, which in free form or as an adduct, together.

    Es ist möglich, die Metallocenverbindung vor dem Einsatz in der Polymerisationsreaktion mit einem Cokatalysator, insbesondere einem Aluminoxan vorzuaktivieren. Dadurch wird die Polymerisationsaktivität deutlich erhöht. Die Voraktivierung der Metallocenverbindung wird vorzugsweise in Lösung vorgenommen. Bevorzugt wird dabei die Metallocenverbindung in einer Lösung des Aluminoxans in einem inerten Kohlenwasserstoff aufgelöst. Als inerter Kohlenwasserstoff eignet sich ein aliphatischer oder aromatischer Kohlenwasserstoff. Bevorzugt wird Toluol verwendet.It is possible to use the metallocene compound in the Polymerization reaction with a cocatalyst, especially one Pre-activate aluminoxane. This makes the polymerization activity clear elevated. The preactivation of the metallocene compound is preferably in Solution made. The metallocene compound is preferred in one Solution of the aluminoxane dissolved in an inert hydrocarbon. As Inert hydrocarbon is an aliphatic or aromatic Hydrocarbon. Toluene is preferably used.

    Die Konzentration des Aluminoxans in der Lösung liegt im Bereich von ca. 1 Gew.-% bis zur Sättigungsgrenze, vorzugsweise von 5 bis 30 Gew.-%, jeweils bezogen auf die Gesamtlösungsmenge. Die Metallocenverbindung kann in der gleichen Konzentration eingesetzt werden, vorzugsweise wird es jedoch in einer Menge von 10-4 bis 1 mol pro mol Aluminoxan eingesetzt. Die Voraktivierungsdauer beträgt 5 Minuten bis 60 Stunden, vorzugsweise 5 bis 60 Minuten. Man arbeitet bei einer Temperatur von -78 bis 150°C, vorzugsweise 0 bis 80°C.The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case based on the total amount of solution. The metallocene compound can be used in the same concentration, but it is preferably used in an amount of 10 -4 to 1 mol per mol of aluminoxane. The preactivation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. One works at a temperature of -78 to 150 ° C, preferably 0 to 80 ° C.

    Die Metallocenverbindung wird bevorzugt in einer Konzentration, bezogen auf das Übergangsmetall, von 10-3 bis 10-8, vorzugsweise 10-4 bis 10-7 mol Übergangsmetall pro dm3 Lösemittel bzw. pro dm3 Reaktorvolumen angewendet. Das Aluminoxan, wird bevorzugt in einer Konzentration von 10-6 bis 10-1 mol, vorzugsweise 10-5 bis 10-2 mol pro dm3 Lösemittel bzw. pro dm3 Reaktorvolumen verwendet. Die anderen genannten Cokatalysatoren werden in etwa äquimolaren Mengen zu der Metallocenverbindung verwendet. Prinzipiell sind aber auch höhere Konzentrationen möglich.The metallocene compound is preferably used in a concentration, based on the transition metal, of 10 -3 to 10 -8 , preferably 10 -4 to 10 -7 mol, transition metal per dm 3 solvent or per dm 3 reactor volume. The aluminoxane is preferably used in a concentration of 10 -6 to 10 -1 mol, preferably 10 -5 to 10 -2 mol per dm 3 of solvent or per dm 3 of reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the metallocene compound. In principle, however, higher concentrations are also possible.

    Das Aluminoxan kann auf verschiedene Arten nach bekannten Verfahren hergestellt werden. Eine der Methoden ist beispielsweise, daß eine Aluminiumkohlenwasserstoffverbindung und/oder eine Hydridoaluminiumkohlenwasserstoffverbindung mit Wasser (gasförmig, fest, flüssig oder gebunden - beispielsweise als Kristallwasser) in einem inerten Lösungsmittel (wie beispielsweise Toluol) umgesetzt wird. Zur Herstellung eines Aluminoxans mit voneinander verschiedenen Resten Rc werden beispielsweise entsprechend der gewünschten Zusammensetzung zwei oder mehrere verschiedene Aluminiumtrialkyle mit Wasser umgesetzt (S. Pazynkiewicz, Polyhedron 9 (1990) 429, EP-A 302 424).The aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene). To produce an aluminoxane with different radicals R c , two or more different aluminum trialkyls are reacted with water, for example in accordance with the desired composition (S. Pazynkiewicz, Polyhedron 9 (1990) 429, EP-A 302 424).

    Unabhängig von der Art der Herstellung ist allen Aluminoxanlösungen ein wechselnder Gehalt an nicht umgesetzter Aluminiumausgangsverbindung, die in freier Form oder als Addukt vorliegt, gemeinsam.Regardless of the type of manufacture, all aluminoxane solutions are one changing content of unreacted aluminum starting compound, which in free form or as an adduct, together.

    Zur Entfernung von im Olefin vorhandenen Katalysatorgiften ist eine Reinigung mit einer Aluminiumverbindung, bevorzugt einem Aluminiumalkyl, wie Trimethylaluminium oder Triethylaluminium, vorteilhaft. Diese Reinigung kann sowohl im Polymerisationssystem selbst erfolgen, oder das Olefin wird vor der Zugabe in das Polymerisationssystem mit der Aluminiumverbindung in Kontakt gebracht und anschließend wieder abgetrennt.Cleaning is required to remove catalyst poisons present in the olefin with an aluminum compound, preferably an aluminum alkyl, such as Trimethyl aluminum or triethyl aluminum, advantageous. This cleaning can both take place in the polymerization system itself, or the olefin is before Added to the polymerization system with the aluminum compound in contact brought and then separated again.

    Bevorzugt wird in dem erfindungsgemäßen Verfahren die Metallocenverbindung mit dem Cokatalysator außerhalb des Polymerisationsreaktors in einem separaten Schritt unter Verwendung eines geeigneten Lösemittels umgesetzt. Dabei kann eine Trägerung vorgenommen werden.The metallocene compound is preferred in the process according to the invention with the cocatalyst outside the polymerization reactor in one separate step using a suitable solvent. Carrying can be carried out.

    Falls dem Reaktionsgemisch Lösemittel zugesetzt wird, dann handelt es sich um gebräuchliche inerte Lösemittel wie z.B. aliphatische oder cycloaliphatische Kohlenwasserstoffe, Benzin- bzw. hydrierte Dieselölfraktionen oder Toluol.If solvent is added to the reaction mixture, then it is common inert solvents such as aliphatic or cycloaliphatic Hydrocarbons, petrol or hydrogenated diesel oil fractions or toluene.

    Die Metallocenverbindung der Formel I wird bevorzugt in Form ihres Racemats eingesetzt. Die Metallocenverbindung wird bevorzugt in einer Konzentration, bezogen auf das Übergangsmetall, von 10-3 bis 10-8, vorzugsweise 10-4 bis 10-7 mol Übergangsmetall pro dm3 Reaktorvolumen angewendet. Das Aluminoxan wird in einer Konzentration von 10-4 bis 10-1, vorzugsweise 10-4 bis 2 * 10-2 mol pro dm3 Reaktorvolumen verwendet, bezogen auf den Gehalt an Aluminium. Prinzipiell sind aber auch höhere Konzentrationen möglich. The metallocene compound of the formula I is preferably used in the form of its racemate. The metallocene compound is preferably used in a concentration, based on the transition metal, of 10 -3 to 10 -8 , preferably 10 -4 to 10 -7 mol, transition metal per dm 3 reactor volume. The aluminoxane is used in a concentration of 10 -4 to 10 -1 , preferably 10 -4 to 2 * 10 -2 mol per dm 3 reactor volume, based on the aluminum content. In principle, however, higher concentrations are also possible.

    In dem erfindungsgemäßen Verfahren wird mindestens ein cyclisches, bevorzugt polycyclisches, Olefin mit mindestens einem acyclischen Olefin polymerisiert. Polycyclische Olefine weisen bevorzugt die Formeln VI, VII, VIII, IX, X oder XI auf

    Figure 00150001
    Figure 00150002
    Figure 00160001
    Figure 00160002
    Figure 00160003
    Figure 00170001
    ,worin R7, R8, R9, R10, R11, R12, R13 und R14 gleich oder verschieden sind und ein Wasserstoffatom oder einen C1-C20-Kohlenwasserstoffrest wie C1-C8-Alkyl oder C6-C10-Aryl bedeuten, oder zwei oder mehr Reste R7-R14 zusammen ein C4-C40-Ringsystem bilden, wobei gleiche Reste R7-R14 in den verschiedenen Formeln eine unterschiedliche Bedeutung haben können. Besonders bevorzugt sind Cycloolefine der Formeln VI oder VIII, worin R7, R8, R9, R10, R11, R12, R13 und R14 gleich oder verschieden sind und ein Wasserstoffatom oder einen C1-C20-Kohlenwasserstoffrest, insbesondere einen C6-C10-Arylrest oder einen C1-C8-Alkylrest bedeuten, wobei gleiche Reste R7-R14 in den verschiedenen Formeln VI - XI eine unterschiedliche Bedeutung haben können.In the process according to the invention, at least one cyclic, preferably polycyclic, olefin is polymerized with at least one acyclic olefin. Polycyclic olefins preferably have the formulas VI, VII, VIII, IX, X or XI
    Figure 00150001
    Figure 00150002
    Figure 00160001
    Figure 00160002
    Figure 00160003
    Figure 00170001
    , wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are the same or different and a hydrogen atom or a C 1 -C 20 hydrocarbon radical such as C 1 -C 8 alkyl or C 6 -C 10 aryl, or two or more radicals R 7 -R 14 together form a C 4 -C 40 ring system, the same radicals R 7 -R 14 having different meanings in the different formulas. Cycloolefins of the formulas VI or VIII, in which R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are identical or different and a hydrogen atom or a C 1 -C 20 hydrocarbon radical are particularly preferred , in particular a C 6 -C 10 aryl radical or a C 1 -C 8 alkyl radical, the same radicals R 7 -R 14 in the different formulas VI-XI having different meanings.

    Acyclische Olefine sind bevorzugt 1-Olefine mit 1 bis 40, vorzugsweise 1 - 20 Kohlenstoffatomen. Besonders bevorzugt sind 1-Olefine der Formel (XII)

    Figure 00180001
    worin R15, R16, R17 und R18 gleich oder verschieden sind und ein Wasserstoffatom oder einen C1-C20-Kohlenwaserstoffrest, bevorzugt einen C6-C10-Arylrest und einen C1-C8-Alkylrest bedeuten. Beispiele für acyclische Olefine sind Ethylen und Propylen.Acyclic olefins are preferably 1-olefins having 1 to 40, preferably 1 to 20, carbon atoms. 1-olefins of the formula (XII) are particularly preferred
    Figure 00180001
    wherein R 15 , R 16 , R 17 and R 18 are the same or different and represent a hydrogen atom or a C 1 -C 20 hydrocarbon radical, preferably a C 6 -C 10 aryl radical and a C 1 -C 8 alkyl radical. Examples of acyclic olefins are ethylene and propylene.

    Gegebenenfalls wird in dem erfindungsgemäßen Verfahren auch eines oder mehrere monocyclische Olefine, insbesondere der Formel (XIII) eingesetzt

    Figure 00180002
    ,worin n eine Zahl von 2 bis 10 ist.If appropriate, one or more monocyclic olefins, in particular of the formula (XIII), are also used in the process according to the invention
    Figure 00180002
    where n is a number from 2 to 10.

    Insbesondere werden Copolymere von polycyclischen Olefinen, vorzugsweise der Formeln VI und VIII, mit Ethylen hergestellt.In particular, copolymers of polycyclic olefins are preferred of the formulas VI and VIII, produced with ethylene.

    Besonders bevorzugte polycyclische Olefine sind Norbornen und Tetracyclododecen, wobei diese durch (C1-C6)-Alkyl substituiert sein können. Sie werden vorzugsweise mit Ethylen copolymerisiert; besondere Bedeutung besitzen Ethylen/Norbornen-Copolymere.Particularly preferred polycyclic olefins are norbornene and tetracyclododecene, which may be substituted by (C 1 -C 6 ) alkyl. They are preferably copolymerized with ethylene; ethylene / norbornene copolymers are particularly important.

    In dem erfindungsgemäßen Verfahren wird bevorzugt das polycyclische Olefin in einer Menge von 0,1 bis 99,9 Gew.-%, das monocyclische Olefin in einer Menge von 0 bis 99,9 Gew.-%, und das acyclische Olefin in einer Menge von 0,1 bis 99,9 Gew.-%, jeweils bezogen auf die Gesamtmenge der Monomeren, eingesetzt.The polycyclic olefin is preferred in the process according to the invention in an amount of 0.1 to 99.9 wt .-%, the monocyclic olefin in one Amount from 0 to 99.9% by weight, and the acyclic olefin in an amount of 0.1 to 99.9% by weight, based in each case on the total amount of the monomers, used.

    Die Konzentration des eingesetzten acyclischen Olefins ergibt sich aus dessen Löslichkeit in dem Reaktionsmedium bei gegebenem Druck und gegebener Temperatur.The concentration of the acyclic olefin used results from this Solubility in the reaction medium at given pressure and given Temperature.

    Als polycyclische Olefine, monocyclische Olefine und acyclische Olefine sind auch Gemische zweier oder mehrerer Olefine des jeweiligen Typs zu verstehen. Das heißt, es können neben polycyclischen Bicopolymeren auch Ter- und Multicopolymere nach dem erfindungsgemäßen Verfahren hergestellt werden. Auch Copolymere monocyclischer Olefine und acyclischer Olefine können nach dem erfindungsgemäßen Verfahren erhalten werden.As polycyclic olefins, monocyclic olefins and acyclic olefins are to understand mixtures of two or more olefins of the respective type. This means that in addition to polycyclic bicopolymers, ter- and Multicopolymers can be produced by the process according to the invention. Copolymers of monocyclic olefins and acyclic olefins can also the method according to the invention can be obtained.

    Von den monocyclischen Olefinen ist Cyclopenten, das substituiert sein kann, bevorzugt.Of the monocyclic olefins, cyclopentene, which can be substituted, is prefers.

    Bevorzugt wird das erfindungsgemäße Verfahren bei Temperaturen von -78 bis 150°C, insbesondere 0 bis 100°C, und einem Druck von 0,01 bis 64 bar durchgeführt.The process according to the invention is preferred at temperatures from -78 to 150 ° C, especially 0 to 100 ° C, and a pressure of 0.01 to 64 bar carried out.

    Die Polymerisation wird im flüssigen Cycloolefin selbst oder in Cycloolefin-Lösung durchgeführt, wobei zweckmäßigerweise der Druck oberhalb 1 bar liegt.The polymerization is carried out in the liquid cycloolefin itself or in cycloolefin solution carried out, wherein the pressure is advantageously above 1 bar.

    Bei der Herstellung von Copolymerisaten kann die Variation der Molverhältnisse des polycyclischen Olefins zum eingesetzten offenkettigen Olefin in einem weiten Bereich erfolgen. Bevorzugt werden molare Verhältnisse von 3:1 bis 100:1 Cycloolefin zu offenkettigem Olefin eingesetzt. Durch die Wahl der Polymerisationstemperatur, durch die Konzentration der Katalysatorkomponenten und das eingesetzte Molverhältnis bzw. den Druck des gasförmigen, offenkettigen Olefins läßt sich die Einbaurate an Comonomer beinahe beliebig steuern. Bevorzugt sind Einbauraten zwischen 20 und 80 Mol-% der cyclischen Komponenten und besonders bevorzugt werden Einbauraten zwischen 40 und 60 Mol-% der cyclischen Komponenten.In the production of copolymers, the variation of the molar ratios can of the polycyclic olefin to the open-chain olefin used in one wide range. Molar ratios of 3: 1 to are preferred 100: 1 cycloolefin used to open-chain olefin. By choosing the Polymerization temperature, by the concentration of the Catalyst components and the molar ratio used or the pressure of the The rate of incorporation of comonomer can be gaseous, open-chain olefins control almost anything. Installation rates between 20 and 80 mol% are preferred of the cyclic components and particularly preferred are installation rates between 40 and 60 mol% of the cyclic components.

    Die Polymerisation kann auch mehrstufig erfolgen, wobei auch Blockcopolymere entstehen können (EP-A-560 090).The polymerization can also be carried out in several stages, including block copolymers can arise (EP-A-560 090).

    Die mittlere Molmasse des gebildeten Polymeren läßt sich weiter durch Wasserstoff-Dosierung, Variation der Katalysatorkonzentration oder Variation der Temperatur in bekannter Weise steuern.The average molecular weight of the polymer formed can be further determined Hydrogen dosing, variation of the catalyst concentration or variation control the temperature in a known manner.

    Die Polydispersität Mw/Mn der Cycloolefincopolymeren ist mit Werten von 1,9 bis 3,5 recht eng. Dadurch resultiert ein Eigenschaftsbild, das diese für das Spritzgießen besonders geeignet macht.The polydispersity M w / M n of the cycloolefin copolymers is quite narrow with values from 1.9 to 3.5. This results in a property profile that makes them particularly suitable for injection molding.

    Mit dem erfindungsgemäßen Verfahren lassen sich amorphe Cycloolefincopolymere herstellen, die keine teilkristallinen Ethylenpolymerisate enthalten. Die Copolymeren sind transparent, hart und thermoplastisch verarbeitbar. Die Reißspannungen (gemäß DIN 53457) liegen im Bereich von 50 bis 100 MPa, bevorzugt zwischen 55 und 70 MPa. Sowohl beim Extrudieren als auch beim Spritzgießen wurden bei Temperaturen von 300°C keine Zersetzungsreaktionen oder ein Viskositätsabbau gefunden.The process according to the invention can be used to produce amorphous cycloolefin copolymers produce that do not contain semi-crystalline ethylene polymers. The copolymers are transparent, hard and thermoplastically processable. The Tensile stresses (according to DIN 53457) are in the range of 50 to 100 MPa, preferably between 55 and 70 MPa. Both when extruding and when Injection molding did not cause decomposition reactions at temperatures of 300 ° C or found a viscosity reduction.

    Die erfindungsgemäß hergestellten Cycloolefincopolymere eignen sich besonders zur Herstellung von Formkörpern wie Extrusionsteilen (z.B. Folien, Schläuchen, Rohren, Stangen und Fasern) oder Spritzgußartikeln beliebiger Form und Größe.
    Die Folien können extrudierte Folien, kalanderte Folien, Gießfilme, mono- und biaxial orientierte Folien oder Mehrschicht-Folien sein und eignen sich insbesondere als Lebensmittelverpackungsfolien oder Blisterverpackungen. Sie weisen eine hohe Wassersperrwirkung und eine geringe Gasdurchlässigkeit auf.     The cycloolefin copolymers produced according to the invention are particularly suitable for the production of moldings such as extrusion parts (for example films, tubes, tubes, rods and fibers) or injection molded articles of any shape and size.
    The films can be extruded films, calendered films, cast films, mono- and biaxially oriented films or multilayer films and are particularly suitable as food packaging films or blister packs. They have a high water barrier effect and low gas permeability.

    Die erfindungsgemäß hergestellten Cycloolefincopolymere eignen sich auch als Additiv in anderen Polymerfolien (insbesondere Polyolefinfolien wie Polypropylenfolien oder Polyethylenfolien) z.B. zum Zwecke der Fließverbesserung, Verbesserung der Lackierbarkeit, E-Modul-Beeinflussung und Herstellung von Opakfolien.The cycloolefin copolymers prepared according to the invention are also suitable as Additive in other polymer films (especially polyolefin films such as Polypropylene films or polyethylene films) e.g. for the purpose of Flow improvement, improvement of paintability, modulus of elasticity and Manufacture of opaque films.

    Eine wichtige Eigenschaft der erfindungsgemäß hergestellten Cycloolefincopolymere ist ihre Transparenz. Dadurch kommt besonders den optischen Anwendungen der extrudierten oder spritzgegossenen Teile aus Cycloolefincopolymeren eine große Bedeutung zu. Der mit einem Abbe-Refraktometer und Mischlicht bestimmte Brechungsindex der in den nachfolgenden Beispielen beschriebenen Reaktionsprodukte liegt im Bereich zwischen 1,520 und 1,555. Nachdem der Brechungsindex sehr nahe an dem von Kronglas (n = 1,51) liegt, können die erfindungsgemäßen Produkte als Glasersatz verschiedene Anwendungen finden wie beispielsweise Linsen, Prismen, Trägerplatten und -folien für optische Datenspeicher, für Videoplatten, für Compact Disks, als Deck- und Fokussierscheiben für Solarzellen, als Deckund Streuscheiben für Leistungsoptiken, als Lichtwellenleiter in der Form von Fasern oder Folien.An important property of those produced according to the invention Cycloolefin copolymers are their transparency. This is especially the reason optical applications of the extruded or injection molded parts Cycloolefin copolymers are of great importance. The one with an Abbe refractometer and mixed light determined refractive index of the in the The reaction products described in the following examples are in the range between 1.520 and 1.555. After the refractive index is very close to that of Kronglas (n = 1.51), the products according to the invention can be used as Glass substitutes find various applications such as lenses, Prisms, carrier plates and foils for optical data storage, for video plates, for compact discs, as cover and focusing disks for solar cells, as cover and Diffusers for power optics, as optical fibers in the form of Fibers or foils.

    In schlagzähmodifizierter Form sind die erfindungsgemäß hergestellten Cycloolefincopolymeren als Strukturwerkstoff in verschiedenen technischen Bereichen einsetzbar (EP-A-566 988 ).Those produced according to the invention are in impact-modified form Cycloolefin copolymers as structural material in various technical Areas can be used (EP-A-566 988).

    Die erfindungsgemäß erhaltenen Cycloolefincopolymere sind auch für die Herstellung von Polymerlegierungen einsetzbar. Die Legierungen können in der Schmelze oder in Lösung hergestellt werden. Die Legierungen weisen jeweils eine für bestimmte Anwendungen günstige Eigenschaftskombination der Komponenten auf. Für Legierungen mit den erfindungsgemäßen Cycloolefincopolymeren sind bevorzugt folgende Polymere einsetzbar: Polyethylen, Polypropylen, (Ethylen-Propylen)-Copolymere, Polybutylen, Pvly-(4-methyl-1-penten), Polyisopren, Polyisobutylen, Naturkautschuk, Poly-(methylmethacrylat), weitere Polymethacrylate, Polyacrylate, (Acrylat-Methacrylat)-Copolymere, Polystyrol, (Styrol-Acrylnitril)-Copolymere, Bisphenol-A-Polycarbonat, weitere Polycarbonate, aromatische Polyestercarbonate, Polyethylenterephthalat, Polybutylenterephthalat, amorphe Polyarylate, Nylon-6, Nylon-66, weitere Polyamide, Polyaramide, Polyetherketone, Polyoxymethylen, Polyoxyethylen, Polyurethane, Polysulfone, Polyethersulfone, Polyvinylidenfluorid.The cycloolefin copolymers obtained according to the invention are also suitable for Production of polymer alloys can be used. The alloys can be used in the Melt or be made in solution. The alloys each have a combination of properties that is favorable for certain applications Components. For alloys with the invention The following polymers can preferably be used as cycloolefin copolymers: Polyethylene, polypropylene, (ethylene-propylene) copolymers, polybutylene, PVC (4-methyl-1-pentene), Polyisoprene, polyisobutylene, natural rubber, poly (methyl methacrylate), further polymethacrylates, polyacrylates, (acrylate methacrylate) copolymers, Polystyrene, (styrene-acrylonitrile) copolymers, bisphenol-A polycarbonate, other polycarbonates, aromatic polyester carbonates, Polyethylene terephthalate, polybutylene terephthalate, amorphous polyarylates, nylon-6, Nylon-66, other polyamides, polyaramides, polyether ketones, polyoxymethylene, Polyoxyethylene, polyurethanes, polysulfones, polyether sulfones, Polyvinylidene fluoride.

    Das erfindungsgemäße Verfahren liefert mit hoher Aktivität insbesondere transparente Cycloolefincopolymere, die hohe Reißfestigkeiten aufweisen.The method according to the invention delivers with high activity in particular transparent cycloolefin copolymers that have high tear strengths.

    Die in den folgenden Beispielen angegebenen Glastemperaturen Tg wurden mittels DSC (Differential Scanning Calorimetry) bei einer Aufheizrate von 20°C/min bestimmt. Die angegebenen Viskositätszahlen wurden gemäß DIN 53728 ermittelt. Die mechanischen Eigenschaften wurden im Zugdehnungsversuch gemessen (DIN 53457, Instron 4302).The glass transition temperatures given in the following examples were Tg by means of DSC (Differential Scanning Calorimetry) at a heating rate of 20 ° C / min determined. The indicated viscosity numbers were according to DIN 53728 determined. The mechanical properties were in Tensile elongation test measured (DIN 53457, Instron 4302).

    Als Maß für die Katalysatoraktivität wird die Ausbeute an Polymer pro Zeiteinheit und pro mmol Metallocen herangezogen: Aktivität = Polymer [g] Zeiteinheit [h] x Menge Metallocen [mmol] = A* The yield of polymer per unit of time and per mmol of metallocene is used as a measure of the catalyst activity: Activity = Polymer [g] Time unit [h] x amount of metallocene [mmol] = A *

    Allgemeine Angaben: Herstellung und Handhabung organometallischer Verbindungen erfolgten unter Ausschluß von Luft und Feuchtigkeit unter Argon-Schutz (Schlenk-Technik). Alle benötigten Lösungsmittel wurden vor Gebrauch durch mehrstündiges Sieden über einem geeigneten Trockenmittel und anschließende Destillation unter Argon absolutiert. General information: Production and handling of organometallic Connections were made in the absence of air and moisture under argon protection (Schlenk technique). All required solvents were checked before use by boiling over a suitable desiccant for several hours and followed by absolute distillation under argon.

    Die Herstellung der als Ausgangsverbindungen eingesetzten Diketone und Ketoaldehyde erfolgte nach literaturbekannten Methoden. Cyclopentadien und Methylcyclopentadien wurden durch Cracken der Dimeren gewonnen und bei - 35°C gelagert.The preparation of the diketones and Ketoaldehyde was carried out according to methods known from the literature. Cyclopentadiene and Methylcyclopentadiene was obtained by cracking the dimers and at - stored at 35 ° C.

    Die Ermittlung des Al/CH3-Verhältnisses im Aluminoxan erfolgte durch Zersetzung der Probe mit H2SO4 und Bestimmung des Volumens der entstehenden Hydrolysegase unter Normalbedingungen sowie durch komplexometrische Titration des Aluminiums in der dann gelösten Probe nach Schwarzenbach.The Al / CH 3 ratio in the aluminoxane was determined by decomposing the sample with H 2 SO 4 and determining the volume of the hydrolysis gases formed under normal conditions, and by complexometric titration of the aluminum in the then dissolved sample according to Schwarzenbach.

    Die Verbindungen wurden mit 1H-NMR, 13C-NMR und IR-Spektroskopie charakterisiert.The compounds were characterized by 1 H-NMR, 13 C-NMR and IR spectroscopy.

    Die nachfolgenden Beispiele sollen die Erfindung näher erläutern:The following examples are intended to explain the invention in more detail:

    Alle Glasgeräte wurden unter Vakuum ausgeheizt und mit Argon gespült. Alle Operationen wurden unter Ausschluß von Feuchtigkeit und Sauerstoff in Schlenkgefäßen durchgeführt. Die verwendeten Lösemittel wurden unter Argon von einer Na/K-Legierung abdestilliert.
    Toluol lösliches Methylalumoxan wurde für die Beispiele zur Polymerisation als 10 Gew.-%ige Toluol-Lösung mit einem mittleren Oligomerisationsgrad von n = 20 eingesetzt (Witco). Gemäß Aluminiumbestimmung beträgt der Gehalt 36 mg Al/ml.    All glassware was heated under vacuum and flushed with argon. All operations were carried out in the absence of moisture and oxygen in Schlenk vessels. The solvents used were distilled off from an Na / K alloy under argon.
    Toluene-soluble methylalumoxane was used for the polymerization examples as a 10% by weight toluene solution with an average degree of oligomerization of n = 20 (Witco). According to aluminum determination, the content is 36 mg Al / ml.

    Beispiel 1example 1 Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propyliden]-zirkoniumBis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (indenyl) propylidene] zirconium

    Eine Lösung des Zirkoniumamids (416 mg, 1.55 mmol) in 25 ml Toluol wird auf - 78°C gekühlt und anschließend mit einer Lösung von 345 mg des Liganden in 10 ml Toluol tropfenweise versetzt. Die Lösung wird auf Raumtemperatur erwärmt und nach 12-stündigem Rühren für 3h auf 80°C erhitzt. Das Lösungsmittel wird im Vakuum entfernt und der Komplex in Form eines gelb-orangen Feststoffs in 99% Ausbeute (613 mg) erhalten.
    1H-NMR (400 MHz, C6D6): [ppm] d = 1.57, 1.89 (s, 6H, C(CH3)2), 2.46, 2.81 (s, 12H, N(CH3)2), 5.29 (m, 1H, CH in C5H4), 5.80 (m, 2H, CH in C5H4 und C9H7), 5.99 (m, 1 H, CH in C5H4), 6.08 (m, 1 H, CH in C5H4), 6.59 (d, 1 H, 3J(H,H) = 3.0 Hz, CH in C9H7), 6.69 (m, 1 H, CH in C9H7), 7.49 (m, 1 H, CH in C9H7), 7.62 (m, 1 H, CH in C9H7).
    MS (CI): m/z (%) = 708 (10) [2M+ - 2 NMe2], 398 (100) [M+], 355 (45) [M+ - NMe2], 311 (21 %) [M+ - 2 NMe2].    A solution of the zirconium amide (416 mg, 1.55 mmol) in 25 ml of toluene is cooled to -78 ° C. and then a solution of 345 mg of the ligand in 10 ml of toluene is added dropwise. The solution is warmed to room temperature and, after stirring for 12 hours, heated to 80 ° C. for 3 hours. The solvent is removed in vacuo and the complex is obtained in the form of a yellow-orange solid in 99% yield (613 mg).
    1 H-NMR (400 MHz, C 6 D 6 ): [ppm] d = 1.57, 1.89 (s, 6H, C (CH 3 ) 2 ), 2.46, 2.81 (s, 12H, N (CH 3 ) 2 ) , 5.29 (m, 1H, C H in C 5 H 4 ), 5.80 (m, 2H, C H in C 5 H 4 and C 9 H 7 ), 5.99 (m, 1 H, C H in C 5 H 4 ), 6.08 (m, 1 H, C H in C 5 H 4 ), 6.59 (d, 1 H, 3 J (H, H) = 3.0 Hz, C H in C 9 H 7 ), 6.69 (m, 1 H, C H in C 9 H 7 ), 7.49 (m, 1 H, C H in C 9 H 7 ), 7.62 (m, 1 H, C H in C 9 H 7 ).
    MS (CI): m / z (%) = 708 (10) [2M + - 2 NMe 2 ], 398 (100) [M + ], 355 (45) [M + - NMe 2 ], 311 (21% ) [M + - 2 NMe 2 ].

    Beispiel 2Example 2 Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propyliden]-hafniumBis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (indenyl) propylidene] hafnium

    Eine Lösung des Hafniumamids (833 mg, 1.55 mmol) in 25 ml Xylol wird auf -78°C gekühlt und anschließend mit einer Lösung von 522 mg des Liganden in 10 ml Xylol tropfenweise versetzt. Die Lösung wird auf Raumtemperatur erwärmt und nach 2-stündigem Rühren für 8h auf 150°C erhitzt. Das Lösungsmittel wird im Vakuum entfernt und der Komplex aus wenig Pentan umkristallisiert. Der Komplex fällt in Form eines gelb-orangen Feststoffs (95% Ausbeute, 613 mg) aus.
    1H-NMR (400 MHz, C6D6): [ppm] d = 1.57, 1.88 (s, 6H, C(CH 3)2), 2.51, 2.85 (s, 12H, N(CH3)2), 5.29 (m, 1 H, CH in C5H4), 5.70 - 5.80 (m, 2H, CH in C5H4 und C9H7), 6.00 (m, 1H, CH in C5H4), 6.04 (m, 1 H, CH in C5H4), 6.53 (d, 1 H, 3J(H,H) = 3.0 Hz, CH in C9H7), 6.71 (m, 1 H, CH in C9H7), 6.87 (m, 1 H, CH in C9H7), 7.49 (m, 1 H, CH in C9H7), 7.63 (m, 1 H, CH in C9H7).
    MS (CI): m/z (%) = 620 (100), 600 (18), 512 (24), 497 (28), 442 (17), 399 (25), 222 (26), 207 (26), 115 (8), 107 (20).    A solution of the hafnium amide (833 mg, 1.55 mmol) in 25 ml of xylene is cooled to -78 ° C. and then a solution of 522 mg of the ligand in 10 ml of xylene is added dropwise. The solution is warmed to room temperature and, after stirring for 2 hours, heated to 150 ° C. for 8 hours. The solvent is removed in vacuo and the complex is recrystallized from a little pentane. The complex precipitates in the form of a yellow-orange solid (95% yield, 613 mg).
    1 H-NMR (400 MHz, C 6 D 6 ): [ppm] d = 1.57, 1.88 (s, 6H, C (C H 3 ) 2 ), 2.51, 2.85 (s, 12H, N (CH 3 ) 2 ), 5.29 (m, 1 H, C H in C 5 H 4 ), 5.70 - 5.80 (m, 2H, C H in C 5 H 4 and C 9 H 7 ), 6.00 (m, 1H, C H in C 5 H 4 ), 6.04 (m, 1 H, C H in C 5 H 4 ), 6.53 (d, 1 H, 3 J (H, H) = 3.0 Hz, C H in C 9 H 7 ), 6.71 ( m, 1 H, C H in C 9 H 7 ), 6.87 (m, 1 H, C H in C 9 H 7 ), 7.49 (m, 1 H, C H in C 9 H 7 ), 7.63 (m, 1 H, C H in C 9 H 7 ).
    MS (CI): m / z (%) = 620 (100), 600 (18), 512 (24), 497 (28), 442 (17), 399 (25), 222 (26), 207 (26 ), 115 (8), 107 (20).

    PolymerisationsbeispielePolymerization Beispiel A:Example A:

    In einem 1,5 dm3-Autoklav, der vorher gründlich mit Ethen gespühlt wurde, werden 600 cm3 einer 85 gew.-%igen Lösung von Norbornen in Toluol vorgelegt. Durch mehrfaches Aufdrücken von Ethen (6 bar) wurde die Lösung mit Ethen gesättigt. In den so vorbereiteten Reaktor wurden im Gegenstrom 5 cm3 toluolische Methylaluminoxanlösung (10,1 Gew.-%ige Methylaluminoxanlösung der Molmasse 1300 g/mol nach kryoskopischer Bestimmung) dosiert und 30 Minuten bei 70°C gerührt. Eine Lösung von 1,5 mg Bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propyliden]-zirkonium (I) in 5 cm3 toluolischer Methylaluminoxanlösung wurde nach 15 minütiger Voraktivierung zugegeben. (Im Falle einer Wasserstoffregelung kann an dieser Stelle Wasserstoff aufgepreßt werden.)600 cm 3 of an 85% strength by weight solution of norbornene in toluene are placed in a 1.5 dm 3 autoclave which has been thoroughly rinsed with ethene beforehand. The solution was saturated with ethene by pressing ethene (6 bar) several times. 5 cm 3 of toluene methylaluminoxane solution (10.1% by weight methylaluminoxane solution with a molecular weight of 1300 g / mol after cryoscopic determination) were metered in countercurrent into the reactor thus prepared and stirred at 70 ° C. for 30 minutes. A solution of 1.5 mg of bis (dimethylamido) [η 5 : η 5 -2,2- (cyclopentadienyl) (indenyl) propylidene] zirconium (I) in 5 cm 3 of toluene methylaluminoxane solution was added after 15 minutes of preactivation. (In the case of hydrogen regulation, hydrogen can be injected at this point.)

    Unter Rühren (750 UPM) wurde eine Stunde bei 70°C polymerisiert, wobei der Ethendruck durch Nachdosieren bei 6 bar gehalten wurde.The mixture was polymerized at 70 ° C. for one hour with stirring (750 rpm), the Ethene pressure was kept at 6 bar by metering.

    Nach Ende der Reaktionszeit wurde das Polymerisationsgemisch in ein Gefäß abgelassen und sofort in 5 dm3 Aceton eingetragen, 10 Minuten gerührt und anschließend das ausgefallene Produkt filtriert. Der Filterkuchen wurde je dreimal abwechselnd mit 10 %iger Salzsäure und Aceton gewaschen. Abschließend wurde mit Wasser neutral gewaschen, der Rückstand in Aceton aufgeschlämmt und erneut filtriert. Das so gereinigte Polymer wurde bei 80°C im Vakuum (0,2 bar) 15 Stunden getrocknet.After the end of the reaction time, the polymerization mixture was drained into a vessel and immediately introduced into 5 dm 3 of acetone, stirred for 10 minutes and then the precipitated product was filtered. The filter cake was washed three times alternately with 10% hydrochloric acid and acetone. Finally, it was washed neutral with water, the residue was slurried in acetone and filtered again. The polymer purified in this way was dried at 80 ° C. in vacuo (0.2 bar) for 15 hours.

    Nach der Trocknung wurden 44 g farbloses Polymer erhalten, welches eine Glastemperatur von 193°C, eine Viskositätszahl von 69 cm3/g, eine Reißspannung von 64 MPa und eine Reißdehnung von 3,3% aufwies. Die Aktivität A* betrug 10842 g Polymer/h x mmol.After drying, 44 g of colorless polymer were obtained, which had a glass transition temperature of 193 ° C., a viscosity number of 69 cm 3 / g, a tensile stress at break of 64 MPa and an elongation at break of 3.3%. The activity A * was 10842 g polymer / hx mmol.

    Beispiel B:Example B

    Beispiel A wurde bei einem Ethylendruck von 18 bar und einer Polyrnersiationstemperatur von 90°C wiederholt.
    Die Ausbeute an gereinigtem und getrocknetem Polymer betrug 152 g. Das Polymer wies eine Glastemperatur von 150°C, eine Viskositätszahl von 70 cm3/g, eine Reißspannung von 62 MPa und eine Reißdehnung von 3,5 %. Die Aktivität A* betrug 56182 g Polymer/h x mmol.    Example A was repeated at an ethylene pressure of 18 bar and a polymerisation temperature of 90 ° C.
    The yield of purified and dried polymer was 152 g. The polymer had a glass transition temperature of 150 ° C., a viscosity number of 70 cm 3 / g, a tensile strength at break of 62 MPa and an elongation at break of 3.5%. The activity A * was 56182 g polymer / hx mmol.

    Beispiel C:Example C

    Es wurde wie in Beispiel B verahren, jedoch wurden als Metallocen 0,5 mg Isopropyliden-bis(1-indenyl)bis(N,N-dimethylamido)zirkonium (II) verwendet. Es wurden 114 g gereinigtes und getrocknetes Polymer erhalten, mit einer Glastemperatur von 143°C, einer Viskositätszahl von 152 cm3/g.The procedure was as in Example B, but 0.5 mg of isopropylidene-bis (1-indenyl) bis (N, N-dimethylamido) zirconium (II) were used as metallocene. 114 g of purified and dried polymer were obtained, with a glass transition temperature of 143 ° C. and a viscosity number of 152 cm 3 / g.

    Beispiel D:Example D

    Es wurde wie in Beispiel A verfahren, jedoch wurden als Metallocen 0,1 mg Dimethylsilandiyl-(9-(2,7-di-tert-butyl)fluorenyl)-cyclopentadienyl-bis(N,N-dimethylamido)zirkonium (III) verwendet. Es wurden 17 g gereinigtes und getrocknetes Polymer erhalten mit einer Glastemperatur von 143°C und einer Viskositätszahl von 267 cm3/g.The procedure was as in Example A, but the metallocene used was 0.1 mg of dimethylsilanediyl- (9- (2,7-di-tert-butyl) fluorenyl) cyclopentadienyl-bis (N, N-dimethylamido) zirconium (III) , 17 g of purified and dried polymer were obtained with a glass transition temperature of 143 ° C. and a viscosity number of 267 cm 3 / g.

    Beispiel E:Example E

    Es wurde wie in Beispiel A verfahren, jedoch wurden als Metallocen 0,2 mg Isopropyliden-(9-fluorenyl)-cyclopentadienyl-bis(N,N-dimethylamido)zirkonium (IV) verwendet. Es wurden 64 g gereinigtes und getrocknetes Polymer erhalten, mit einer Glastemperatur von 151 °C und einer Viskositätszahl von 147 cm3/g.

    Figure 00270001
    The procedure was as in Example A, but 0.2 mg of isopropylidene (9-fluorenyl) cyclopentadienyl-bis (N, N-dimethylamido) zirconium (IV) was used as the metallocene. 64 g of purified and dried polymer were obtained, with a glass transition temperature of 151 ° C. and a viscosity number of 147 cm 3 / g.
    Figure 00270001

    Claims (20)

    1. Process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula (I),
      Figure 00360001
      where L and L' are each a substituted or unsubstituted cyclopentadienyl group, T is a bridge between L and L' and is (R5R6X]n, where X are each, independently of one another, carbon, silicon, germanium or tin, the radicals R5 and R6 are each, independently of one another, a hydrogen atom or a C1-C30-hydrocarbon radical and n is 1, 2, 3 or 4, M is a tetravalent transition metal and R1, R2, R3 and R4 are identical or different and are each, independently of one another, a hydrogen atom or a C1-C20-hydrocarbon radical.
    2. Process according to Claim 1, wherein the radicals R5 and R6 are each a hydrogen atom, C1-C20-alkyl or C6-C20-aryl.
    3. Process according to Claim 1 or 2, wherein the bridge T is a radical selected from the group consisting of dimethylsilanediyl, methylphenylsilanediyl, diphenylsilanediyl, dimethylgermanediyl, 1,2-tetramethyldisilanediyl, 1,2-ethylidene, 1,2-propylidene, 1,2-butylidene, 1,3-propylidene, 1,4-butylidene and 2,2-propylidene.
    4. Process according to one or more of Claims 1 to 3, wherein L and L' are each, independently of one another, cyclopentadienyl, tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-a-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.
    5. Process for preparing a cycloolefin copolymer by polymerization of at least one cyclic olefin and at least one acyclic olefin in the presence of a catalyst comprising at least one metallocene compound of the formula (II),
      Figure 00380001
      where Cp is an unsubstituted or substituted cyclopentadiene group, Ind is an unsubstituted or substituted indenyl, the radicals R5 and R6 are identical or different and are each, independently of one another, a hydrogen atom or a C1-C30-hydrocarbon radical and n is 1, 2, 3 or 4, M is a tetravalent transition metal and R1, R2, R3 and R4 are identical or different and are each, independently of one another, a hydrogen atom or a C1-C20-hydrocarbon radical.
    6. Process according to Claim 4, wherein Cp is the radical cyclopentadienyl, tetramethylcyclopentadienyl, methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, isopropylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, trimethylethylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-α-acenaphthindenyl, 2-methyl-4,6-diisopropylindenyl, fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl and Ind is the radical, indenyl, 2-methylindenyl, 2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl, 4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl, 2-methyl-α-acenaphthindenyl or 2-methyl-4,6-diisopropylindenyl.
    7. Process according to one or more of Claims 1 to 6, wherein the catalyst further comprises at least one cocatalyst.
    8. Process according to Claim 7, wherein the cocatalyst is an aluminium compound and/or a boron compound.
    9. Process according to Claim 8, wherein the cocatalyst is an aluminoxane.
    10. Process according to one or more of Claims 1 to 9, wherein the metallocene compound of the formula I is one of the following compounds:
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propylidene)]zirconium
      bis(dimethylamido) [η5:η5-2,2-(cyclopentadienyl)(indenyl)propylidene)]hafnium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(fluorenyl)propylidene)]hafnium
      bis (dimethylamido) [η5:η5-2,2-(fluorenyl)(indenyl)propylidene)]zirconium
      bis(dimethylamido) [η5:η5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium
      bis (dimethylamido) [η5:η5-2,2-(methylcyclopentadienyl)(indenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(fluorenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(2-methylindenyl)(propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(tetramethylcyclopentadienyl)(indenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)-(2-methylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)-(2-ethylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)-(3-trimethylsilyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-methylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl)propylidene)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-(cyclopentadienyl)(indenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-(fluorenyl)(indenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-(methylcyclopentadienyl)(indenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-(methylcyclopentadienyl)(fluorenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(fluorenyl)(2-methylindenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(tetramethylcyclopentadienyl)(indenyl))]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(tetramethylcyclopentadienyl)(fluorenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(fluorenyl)(2-ethylindenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(2,2-(cyclopentadienyl)(2-methylindenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(cyclopentadienyl)(2-ethylindenyl)]zirconium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(cyclopentadienyl)(trimethylsilylindenyl))]zirconnium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(methylcyclopentadienyl)(2-methylindenyl))]zirconnium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(methylcyclopentadienyl)(2-ethylindenyl))]zirconnium
      bis(dimethylamido)[dimethylsilanediyl(η5:η5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl))]zirconium
      stanntetraylbis(η5:η5-bis(cyclopentadienyl)-bis-(dimethylamido)zirconium]
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(indenyl)propylidene)]hafnium
      bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(indenyl)propylidene]zirconium
      bis (dimethylamido) [η5:η5-2,2-(fluorenyl)(indenyl)propylidene)]hafnium
      bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(indenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(2-methylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(tetramethylcyclopentadienyl)(indenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(fluorenyl)(2-ethylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(2-methylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(2-ethylindenyl)propylidene)]zirconium
      bis(dimethylamido)[η5:η5-2,2-(cyclopentadienyl)(3-trimethylsilylindenyl)propylidene]zirconium
      bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-methylindenyl)propylidene)zirconium
      bis(dimethylamido)[η5:η5-2,2-(methylcyclopentadienyl)(2-ethylindenyl)propylidene]zirconium
      bis (dimethylamido) [η5:η5-2,2-(methylcyclopentadienyl)(3-trimethylsilylindenyl)propylidene]zirconium
      bis (dimethylamido) [η5:η5-2,2-(2-methylindenyl)-(indenyl)propylidene]zirconium
      bis(dimethylamido)[η5:η5-2,2-bis(indenyl)propylidene)]zirconium.
    11. Process according to one or more of Claims 1 to 10, wherein M is titanium, zirconium or hafnium.
    12. Process according to one or more of Claims 1 to 11, wherein R1, R2, R3 and R4 are identical and are , each C1-C20-alkyl or C6-C14-aryl.
    13. Process according to one or more of Claims 1 to 12, wherein R1, R2, R3 and R4 are each methyl .
    14. Process according to one or more of Claims 1 to 13, wherein the cyclic olefin is a polycyclic olefin having one of the formulae VI to XI,
      Figure 00420001
      Figure 00420002
      Figure 00430001
      Figure 00430002
      Figure 00430003
      Figure 00430004
      where R7, R8, R9, R10, R11, R12, R13 and R14 are identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical such as C1-C8-alkyl or C6-C10-aryl or two or more radicals R7-R14 together form a C4-C40 ring system, where the same radicals R7-R14 in the various formulae can have different meanings.
    15. Process according to one or more of Claims 1 to 14, wherein the acyclic olefin is a 1-olefin having 1-20 carbon atoms.
    16. Process according to one or more of Claims 1 to 15, wherein the acyclic'olefin is a 1-olefin of the formula XII,
      Figure 00440001
      where R15, R16, R17 and R18 are identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical.
    17. Process according to one or more of Claims 1 to 16, wherein the cyclic olefin is an olefin of the formula VI or VIII and the acyclic olefin is ethylene.
    18. Process according to one or more of Claims 1 to 17, wherein the cyclic olefin is norbornene.
    19. Process according to one or more of Claims 1 to 18, wherein one or more monocyclic olefins of the formula XIII
      Figure 00450001
         where n is from 2 to 10, are additionally used.
    20. Process according to Claim 19, wherein the monocyclic olefin is cyclopentene, which may be substituted.
    EP96119751A 1995-12-13 1996-12-10 Process for preparation of cycloolefin copolymers Expired - Lifetime EP0779306B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19546500A DE19546500A1 (en) 1995-12-13 1995-12-13 Production of cyclo-olefin copolymers e.g. for pipes
    DE19546500 1995-12-13

    Publications (3)

    Publication Number Publication Date
    EP0779306A2 EP0779306A2 (en) 1997-06-18
    EP0779306A3 EP0779306A3 (en) 1999-03-03
    EP0779306B1 true EP0779306B1 (en) 2003-12-03

    Family

    ID=7779982

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP96119751A Expired - Lifetime EP0779306B1 (en) 1995-12-13 1996-12-10 Process for preparation of cycloolefin copolymers

    Country Status (8)

    Country Link
    US (2) US5869586A (en)
    EP (1) EP0779306B1 (en)
    JP (1) JPH09176223A (en)
    KR (1) KR100480532B1 (en)
    CN (1) CN1089771C (en)
    CA (1) CA2192771C (en)
    DE (2) DE19546500A1 (en)
    TW (1) TW356473B (en)

    Families Citing this family (74)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6169152B1 (en) * 1996-07-05 2001-01-02 Jsr Corporation Olefin polymerization catalyst comprising transition metal compound containing a cyclic ligand having at least two nitrogen atoms in its main chain skeleton
    JP3566819B2 (en) * 1996-10-04 2004-09-15 関東化学株式会社 New organic transition metal compounds
    DE19652340A1 (en) * 1996-12-17 1998-06-18 Hoechst Ag Process for the preparation of cycloolefin copolymers
    US6517781B1 (en) * 1997-06-02 2003-02-11 Aurora Biosciences Corporation Low fluorescence assay platforms and related methods for drug discovery
    US6096677A (en) * 1997-10-17 2000-08-01 Sri International Supported metallocene catalysts
    US5892079A (en) * 1997-10-17 1999-04-06 Sri International Metallocene catalysts and associated methods of preparation and use
    US5986024A (en) * 1997-10-17 1999-11-16 Sri International Preparation of multimodal polymer compositions using multinuclear metallocene catalysts
    JPH11281351A (en) * 1998-01-28 1999-10-15 Fuji Electric Co Ltd Distance measuring apparatus
    EP0933383A1 (en) * 1998-01-29 1999-08-04 Union Carbide Chemicals & Plastics Technology Corporation Catalyst composition for the polymerization of olefins
    US6861035B2 (en) * 1998-02-24 2005-03-01 Aurora Discovery, Inc. Multi-well platforms, caddies, lids and combinations thereof
    EP0965614B1 (en) 1998-06-16 2006-03-15 Ticona GmbH Impact resistant cycloolefin-copolymer blend
    US6228790B1 (en) * 1998-06-29 2001-05-08 Industrial Technology Research Institute Dinuclear metallocene catalyst for preparing high molecular weight olefin polymer
    WO2000002891A1 (en) 1998-07-10 2000-01-20 Exxon Chemical Patents Inc. Tethered monocyclopentadienyl polymerization catalysts
    EP0985677A1 (en) * 1998-09-07 2000-03-15 Industrial Technology Research Institute Dinuclear metallocene catalyst for olefin polymerization
    GB9826874D0 (en) * 1998-12-07 1999-01-27 Borealis As Process
    US6339035B1 (en) * 1999-02-22 2002-01-15 Phillips Petroleum Company Catalyst and process for polymerizing olefins
    DE19929809A1 (en) 1999-06-30 2001-01-04 Ticona Gmbh Continuous process for the production of an amorphous polyolefin with a broad molar mass distribution and uniform glass temperature
    DE19932384A1 (en) * 1999-07-14 2001-01-18 Mitsubishi Polyester Film Gmbh White, biaxially oriented polyester film with cycloolefin copolymer (COC), process for its production and its use
    US6544919B1 (en) 1999-10-06 2003-04-08 Sri International Multinuclear transition metal catalysts for preparation of multimodal polymer compositions
    KR100416470B1 (en) * 1999-12-20 2004-01-31 삼성아토피나주식회사 Ethylene-Aromatic Vinyl Compound-Vinyl Norbonene Terpolymer
    US6420047B2 (en) * 2000-01-21 2002-07-16 Cyclics Corporation Macrocyclic polyester oligomers and processes for polymerizing the same
    US6960626B2 (en) * 2000-01-21 2005-11-01 Cyclics Corporation Intimate physical mixtures containing macrocyclic polyester oligomer and filler
    US6906147B2 (en) * 2002-03-20 2005-06-14 Cyclics Corporation Catalytic systems
    US7256241B2 (en) * 2000-01-21 2007-08-14 Cyclics Corporation Methods for polymerizing macrocyclic polyester oligomers using catalyst promoters
    US20050282952A1 (en) * 2000-01-21 2005-12-22 Cyclics Corporation Graphite-polyester composites made from macrocyclic polyester oligomers
    US7151143B2 (en) * 2000-01-21 2006-12-19 Cyclics Corporation Blends containing macrocyclic polyester oligomer and high molecular weight polymer
    DE10003934A1 (en) * 2000-01-29 2001-08-09 Daimler Chrysler Ag Light guide, comprises at least one optical fiber made of cycloolefin copolymer with impeded crystallization
    US6497676B1 (en) 2000-02-10 2002-12-24 Baxter International Method and apparatus for monitoring and controlling peritoneal dialysis therapy
    DE10009286A1 (en) * 2000-02-28 2001-08-30 Mitsubishi Polyester Film Gmbh White, biaxially-oriented, fire-resistant, UV-stabilised polyester film, used e.g. for packaging light- or air-sensitive food, has at least one layer containing cyclo-olefin copolymer, UV stabiliser and fire retardant
    DE10011652A1 (en) * 2000-03-10 2001-09-13 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film with high whiteness, process for its production and its use
    US6875719B2 (en) * 2000-04-27 2005-04-05 Industrial Technology Research Institute Catalyst composition for preparing olefin polymers
    US20020147104A1 (en) * 2000-04-27 2002-10-10 Industrial Technology Research Institute Catalyst composition for preparing olefin polymers
    DE10026177A1 (en) * 2000-05-26 2001-11-29 Mitsubishi Polyester Film Gmbh White, high-gloss polyester film containing cycloolefin copolymer (COC), process for its production and its use
    DE10030235A1 (en) * 2000-06-20 2002-01-03 Mitsubishi Polyester Film Gmbh White, sealable, thermoformable, biaxially oriented and coextruded polyester film with cycloolefin copolymer, process for its production and its use
    EP1179554A1 (en) * 2000-08-08 2002-02-13 Industrial Technology Research Institute Catalyst composition for preparing olefin polymers
    US7767781B2 (en) 2000-09-01 2010-08-03 Cyclics Corporation Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom
    US7750109B2 (en) 2000-09-01 2010-07-06 Cyclics Corporation Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer
    JP2004507599A (en) * 2000-09-01 2004-03-11 サイクリクス　コーポレイション Method for converting linear polyester into macrocyclic oligoester composition and macrocyclic oligoester
    US6372848B1 (en) 2000-10-10 2002-04-16 Baxter International Inc. Blend of ethylene and α-olefin copolymers obtained using a metallocene catalyst for fabricating medical films and tubings
    KR100417037B1 (en) * 2000-12-22 2004-02-05 이동호 Method for preparing cycloolefin copolymer having desirable material properties
    US6696524B2 (en) 2001-02-20 2004-02-24 E. I. Du Pont De Nemours And Company Low Tg ethylene-based polymer, cycloolefin polymer blends
    US6670423B2 (en) 2001-02-20 2003-12-30 E. I. Du Pont De Nemours And Company Polar ethylene-based polymer, cycloolefin polymer blends
    JP2002338617A (en) * 2001-05-22 2002-11-27 Sumitomo Chem Co Ltd Catalyst component for vinyl compound polymerization, vinyl compound polymerization catalyst, production method for vinyl compound polymer, and using method for transition metal compound
    US7304123B2 (en) * 2001-06-27 2007-12-04 Cyclics Corporation Processes for shaping macrocyclic oligoesters
    EP1409475B1 (en) * 2001-06-27 2005-10-05 Cyclics Corporation Isolation, formulation, and shaping of macrocyclic oligoesters
    US20030077466A1 (en) * 2001-10-19 2003-04-24 Smith Sidney T. Multilayered polymer structure
    EP1456027B1 (en) * 2001-12-21 2009-04-29 E.I. Du Pont De Nemours And Company Multilayer film
    US20030125662A1 (en) * 2002-01-03 2003-07-03 Tuan Bui Method and apparatus for providing medical treatment therapy based on calculated demand
    US7238164B2 (en) 2002-07-19 2007-07-03 Baxter International Inc. Systems, methods and apparatuses for pumping cassette-based therapies
    US6831188B1 (en) 2002-07-31 2004-12-14 Albemarle Corporation Dihydrocarbylamino metal compounds
    AU2003259792A1 (en) * 2002-09-12 2004-04-30 Dow Global Technologies Inc. Preparation of metal complexes
    AU2003259791A1 (en) * 2002-09-12 2004-04-30 Dow Global Technologies Inc. Preparation of metal amide complexes
    KR100576971B1 (en) * 2002-09-13 2006-05-10 금호석유화학 주식회사 A method for producing dinuclear transition metal complexes as olefin polymerization catalyst
    DE60326151D1 (en) 2002-09-17 2009-03-26 Dow Global Technologies Inc IMPROVED METHOD FOR THE PRODUCTION OF POLYMERS
    US7037989B2 (en) * 2003-05-27 2006-05-02 Exxonmobil Chemical Patents Inc. Copolymers of ethylene and/or α-olefins and vicinally disubstituted olefins
    ES2349641T3 (en) * 2003-09-26 2011-01-07 Lubrizol Advanced Materials, Inc. TRANSPARENT THERMOPLASTIC MIXTURE OF A CYCLOLEFINE COPOLYMER AND A THERMOPLASTIC POLYURETHANE.
    TWI356073B (en) 2003-09-26 2012-01-11 Lubrizol Advanced Mat Inc A transparent thermoplastic blend of a cycloolefin
    EP1694771B1 (en) * 2003-12-19 2010-03-10 Cyclics Corporation Processes for dispersing an impact modifier in a macrocyclic polyester oligomer
    US20050209563A1 (en) * 2004-03-19 2005-09-22 Peter Hopping Cassette-based dialysis medical fluid therapy systems, apparatuses and methods
    WO2006100974A1 (en) * 2005-03-18 2006-09-28 Mitsui Chemicals, Inc. Resin composition for solar cell package
    JP4830800B2 (en) * 2006-11-09 2011-12-07 Ｊｓｒ株式会社 Manufacturing method of thin optical lens molding
    US7998115B2 (en) * 2007-02-15 2011-08-16 Baxter International Inc. Dialysis system having optical flowrate detection
    US7731689B2 (en) 2007-02-15 2010-06-08 Baxter International Inc. Dialysis system having inductive heating
    US8361023B2 (en) * 2007-02-15 2013-01-29 Baxter International Inc. Dialysis system with efficient battery back-up
    US8558964B2 (en) 2007-02-15 2013-10-15 Baxter International Inc. Dialysis system having display with electromagnetic compliance (“EMC”) seal
    US8870812B2 (en) 2007-02-15 2014-10-28 Baxter International Inc. Dialysis system having video display with ambient light adjustment
    US7863210B2 (en) 2007-12-28 2011-01-04 Chevron Phillips Chemical Company Lp Nano-linked metallocene catalyst compositions and their polymer products
    US8012900B2 (en) * 2007-12-28 2011-09-06 Chevron Phillips Chemical Company, L.P. Nano-linked metallocene catalyst compositions and their polymer products
    US8080681B2 (en) * 2007-12-28 2011-12-20 Chevron Phillips Chemical Company Lp Nano-linked metallocene catalyst compositions and their polymer products
    WO2009108930A1 (en) 2008-02-29 2009-09-03 Albemarle Corporation Processes for producing transition metal amido and imido compounds
    US7919639B2 (en) 2009-06-23 2011-04-05 Chevron Phillips Chemical Company Lp Nano-linked heteronuclear metallocene catalyst compositions and their polymer products
    WO2013116445A1 (en) 2012-01-31 2013-08-08 E. I. Du Pont De Nemours And Company Multilayer film comprising cyclic olefin copolymer
    CN109071850B (en) 2016-05-12 2021-04-27 沙特基础工业全球技术有限公司 Capacitor film with high temperature resistance, manufacturing method thereof and product thereof
    US11179516B2 (en) 2017-06-22 2021-11-23 Baxter International Inc. Systems and methods for incorporating patient pressure into medical fluid delivery

    Family Cites Families (21)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    ZA844157B (en) 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
    US5324800A (en) * 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
    PL276385A1 (en) 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
    IL85097A (en) 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
    US5003019A (en) * 1987-03-02 1991-03-26 Mitsui Petrochemical Industries, Ltd. Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers
    DE3726067A1 (en) 1987-08-06 1989-02-16 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
    DE3922546A1 (en) 1989-07-08 1991-01-17 Hoechst Ag METHOD FOR THE PRODUCTION OF CYCLOOLEFINPOLYMERS
    ES2087145T3 (en) 1989-10-10 1996-07-16 Fina Technology METALLOCAN CATALYSTS WITH LEWIS ACIDS AND ALKYL-ALUMINUMS.
    ES2086397T5 (en) 1989-10-30 2005-07-16 Fina Technology, Inc. ADDITION OF ALKILOALUMINIO FOR AN IMPROVED METALOCENE CATALYST.
    US5371158A (en) * 1990-07-05 1994-12-06 Hoechst Aktiengesellschaft Bulk polymerization using specific metallocene catalysts for the preparation of cycloolefin polymers
    ATE166895T1 (en) * 1991-03-09 1998-06-15 Targor Gmbh METHOD FOR PRODUCING CHEMICALLY UNIFORM CYCLOOLEFIN COPOLYMERS
    TW312695B (en) 1992-02-22 1997-08-11 Hoechst Ag
    TW286324B (en) 1992-04-22 1996-09-21 Hoechst Ag
    IT1256603B (en) 1992-10-30 1995-12-12 Enichem Polimeri CATALYST AND PROCEDURE FOR (CO) POLYMERIZING ALPHA-OLEFINS
    DE59402624D1 (en) * 1993-02-12 1997-06-12 Hoechst Ag Process for the preparation of cycloolefin copolymers
    DE4304291A1 (en) * 1993-02-12 1994-08-18 Hoechst Ag Cycloolefin copolymers with low melt viscosity and low optical attenuation
    EP0610843B1 (en) * 1993-02-12 1999-05-19 Ticona GmbH Process for preparing cyclo-olefin polymers
    DE4304311C2 (en) * 1993-02-12 1998-08-06 Hoechst Ag Cycloolefin copolymers for extrusion and injection molding articles and process for the preparation of a cycloolefin copolymer
    FI945959A (en) * 1993-12-21 1995-06-22 Hoechst Ag Metallocenes and their use as catalysts
    US5597935A (en) * 1994-06-01 1997-01-28 University Of Iowa Research Foundation Synthesis of ansa-metallocene catalysts
    DE4422157A1 (en) * 1994-06-24 1996-01-04 Hoechst Ag Process for the preparation of cycloolefin copolymers

    Also Published As

    Publication number Publication date
    KR970042568A (en) 1997-07-24
    US5869586A (en) 1999-02-09
    CN1151995A (en) 1997-06-18
    US6020444A (en) 2000-02-01
    TW356473B (en) 1999-04-21
    CA2192771A1 (en) 1997-06-14
    KR100480532B1 (en) 2005-07-07
    EP0779306A3 (en) 1999-03-03
    JPH09176223A (en) 1997-07-08
    DE59610845D1 (en) 2004-01-15
    DE19546500A1 (en) 1997-06-19
    CA2192771C (en) 2007-03-27
    CN1089771C (en) 2002-08-28
    EP0779306A2 (en) 1997-06-18

    Similar Documents

    Publication Publication Date Title
    EP0779306B1 (en) Process for preparation of cycloolefin copolymers
    EP0659758B1 (en) Metallocenes and their use as catalysts
    EP0690078B1 (en) Cycloolefin polymers
    EP0610843B1 (en) Process for preparing cyclo-olefin polymers
    EP0610851B1 (en) Process for preparing cyclo-olefin copolymers
    EP0729977B1 (en) Metallocene and catalyst
    EP0501370B1 (en) Process for preparing cyclo-olefinic(co)polymers with a narrow molecular weigth distribution
    EP0688801B1 (en) Process for preparing cycloolefin copolymers
    EP0485893B1 (en) Bulk polymerisation with metallocene catalyst for the preparation of cycloolefin polymers
    EP0946618B1 (en) Cycloolefin polymers, their use and moulding prepared therefrom
    EP0946616B1 (en) Method for producing a cycloolefin copolymer
    EP0749988A2 (en) Process for the preparation of cycloolefin copolymers
    EP0610850A1 (en) Process for preparing cyclo-olefin polymers
    DE4344631A1 (en) Stereo-rigid metallocenes useful in catalyst for cyclo-olefin copolymer prodn.
    EP0694557A2 (en) Organo metallic compounds
    DE4432617A1 (en) Stereo-rigid metallocenes useful in catalyst for cyclo-olefin copolymer prodn.

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): DE FR GB IT NL

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: MITSUI PETROCHEMICAL INDUSTRIES, LTD.

    Owner name: TICONA GMBH

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: MITSUI PETROCHEMICAL INDUSTRIES, LTD.

    Owner name: TICONA GMBH

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): DE FR GB IT NL

    17P Request for examination filed

    Effective date: 19990903

    17Q First examination report despatched

    Effective date: 20000904

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: MITSUI PETROCHEMICAL INDUSTRIES, LTD.

    Owner name: TICONA GMBH

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): DE FR GB IT NL

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REF Corresponds to:

    Ref document number: 59610845

    Country of ref document: DE

    Date of ref document: 20040115

    Kind code of ref document: P

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20040303

    ET Fr: translation filed
    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20040906

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20151211

    Year of fee payment: 20

    Ref country code: GB

    Payment date: 20151221

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: NL

    Payment date: 20151221

    Year of fee payment: 20

    Ref country code: FR

    Payment date: 20151221

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20151228

    Year of fee payment: 20

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R071

    Ref document number: 59610845

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: MK

    Effective date: 20161209

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: PE20

    Expiry date: 20161209

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20161209